Thesis (Ph. D.)--Earth and Atmospheric Sciences, Georgia Institute of Technology, 2007. / Dr. Greg Huey, Committee Chair ; Dr. Paul Wine, Committee Member ; Dr. Rodney Weber, Committee Member ; Dr. David Tan, Committee Member ; Dr. Robert Whetten, Committee Member.

Thesis (Ph. D.)--University of Pennsylvania, 1904. / Includes bibliographical references.

Formic acid and nitric acid have been found to contribute to aerosol formation and are key components of acidity in the troposphere. Tropospheric measurements of these species are often limited, resulting in major uncertainties when assessing their effects on the climate. Current global chemistry-transport models significantly under-predict formic acid concentrations, particularly in the mid-to-high latitudes of the Northern Hemisphere. Furthermore, large discrepancies exist in the role played by dinitrogen pentoxide on nitric acid production between two recently documented models assessing the global nitric acid budget. In order to accurately constrain the budget of these acids in the mid-to-high latitudes of the Northern Hemisphere, it is crucial that these uncertainties are addressed. In this work, airborne measurements of formic acid, nitric acid and dinitrogen pentoxide are presented from across different regions of the Northern Hemisphere to investigate direct and indirect sources contributing to the formic acid and nitric acid regional budgets. Measurements were collected using a Chemical Ionisation Mass Spectrometer (CIMS) fitted to the Facility for Atmospheric Airborne Measurements (FAAM) BAe-146 aircraft. Formic acid measurements within the European Arctic during March and July 2012 would indicate ocean sources dominate over terrestrial sources irrespective of seasonality. CH2I2 photolysis and oxidation was hypothesised as a marine source of formic acid. Modelled estimates would indicate the CH2I2 reaction route may represent a significant summer marine source of formic acid within the Fenno-Scandinavian Arctic. Additionally, low altitude aircraft measurements taken within the Fenno-Scandinavian Arctic over regions occupied by wetlands in August 2013 were used to calculate a formic acid surface flux. Results would suggest formic acid emission from wetlands may represent up to 37 times greater than its globally inferred estimate. A flux measurement conducted over a comparable region in September 2013 observed a negative flux, indicating a change of this region from a net source to a net sink of formic acid. The inconsistency of this regional wetland source confirms the need for in-depth studies on formic acid emission from wetlands, in order to better understand its contribution to the regional and global formic acid budget. In a separate study, significant daytime elevations of N2O5 and HNO3 concentrations were observed within identified biomass burning plumes off the eastern coast of Canada. In-plume correlations between N2O5 and HNO3 concentrations observed within these environments suggest N2O5 was acting as additional daytime source of gaseous HNO3 when subjected to photolytically-limited conditions. This result has important implications to ozone production and provides evidence for an additional daytime source of nitric acid, which must be included in chemistry models calculating the global nitric acid budget.

Recent field campaigns have measured enhanced levels of NOx (NO+NO2) and HOx precursors (i.e., H2O2, CH2O, and HONO) that can not be accounted for by gas phase chemistry alone. Snowpack emission is now considered a source of these species. Therefore, the photochemistry in the polar boundary layer is now believed to be much more complex than initially thought. Field campaigns to Summit, Greenland in the summer of 2003 and the spring of 2004 have obtained the first measurements of peroxy (HO2+RO2) and hydroxyl (OH) radicals in the Artic boundary layer. Measurements were collected with a chemical ionization mass spectrometer (CIMS). A highly constrained (ie., O3, H2O, CH4, CO, j-values, NO, H2O2,CH2O, and HONO) 0-D steady-state model was employed in order to test our current understanding of photochemistry. HO2+RO2 measurements were in excellent agreement with model predictions for both spring and summer. OH measurements were in good agreement with spring model predictions but were a factor of two greater than summer model predictions. The role of snowpack emission is also addressed in a HOx budget performed on the spring campaign. Measurements of nitric acid (HNO3) and pernitric acid (HO2NO2) were obtained with the CIMS during the Antarctic Tropospheric Chemistry Investigation (ANTCI). The linkage between HOx and NOx chemistry is examined through partitioning of reactive nitrogen between HNO3 and HO2NO2. The possible impact of reactive nitrogen partitioning on nitrate ions (NO3-) at coring sites is also investigated.

Industrial activities of mankind are feared to damage the environment irretrievably. Especially the release of huge amounts of harmful gases causes concern. In this regard the environmental pollution caused by the one billion motor vehicles on earth is particularly important. The platinum-group metals (PGM) are well known for their catalytic activity. They are used extensively for reducing the amounts of hydrocarbons, carbon monoxide and nitrogen oxides from the exhausts gas emitted by automobiles. In 2012 20% of platinum and 27% of palladium produced were used in the manufacture of catalytic converters. With the increasing use of PGM-containing autocatalysts, the reclaiming of PGMs from spent catalysts has become essential. Particularly attractive hydrometallurgical methods are those based on the use of halide ions e.g. sodium chloride, as complexing agent in conjunction with nitric acid as oxidant. The chemical reactions between mixtures of aluminium chloride and nitric acid have been studied, but the electrochemical reactions have received little attention. The research reported in this dissertation is aimed at providing data relating to the electrochemical behaviour of platinum in mixtures of aluminium chloride and nitric acid. The construction of Pourbaix diagrams of platinum in chloride environments confirmed that the stable chloro-complexes [PtCl4]2- and PtCl6]2-, as well as platinum oxides (PtO and PtO2) could play a role under the experimental conditions employed in this study. From the thermodynamic results it can be concluded that the systems deserving consideration favour high chloride concentrations and high temperatures. Notable anodic reactions found were the adsorption of chloride on the platinum surface and the gradual formation of [PtCl6]2-, followed by the formation of platinum oxides at 1.00 to 1.01 V. The results show that anodic currents diminished with lower chloride concentrations. A seemingly anomalous anodic behaviour at 35 °C and 45 °C could be explained in terms of a competition between platinum oxide formation and the formation of platinum chloro-complexes. Evidence for the following cathodic reduction reactions was found: hydrogen evolution, reduction of dissolved oxygen to hydrogen dioxide (-1.3 V SHE), nitrate ion reduction to nitrite ions (-0.01 V SHE), nitrite ion reduction to nitric oxide (-0.85 V SHE) and reduction of PtO and PtO2 to Pt (at -1.00 V and 1.01 V SHE, respectively). A brief study was undertaken in an attempt to relate the electrochemical results to the leaching of platinum from a virgin automotive exhaust catalyst. The recovery was low for mixtures with low chloride concentrations, which could be expected from the electrochemical polarisation curves obtained in electrolytes with different chloride concentrations. The maximum platinum recovery attained, was 60% at 45 °C in a mixture containing 0.6 M AlCl3 and 0.9 M HNO3. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

Industrial activities of mankind are feared to damage the environment irretrievably. Especially the release of huge amounts of harmful gases causes concern. In this regard the environmental pollution caused by the one billion motor vehicles on earth is particularly important. The platinum-group metals (PGM) are well known for their catalytic activity. They are used extensively for reducing the amounts of hydrocarbons, carbon monoxide and nitrogen oxides from the exhausts gas emitted by automobiles. In 2012 20% of platinum and 27% of palladium produced were used in the manufacture of catalytic converters. With the increasing use of PGM-containing autocatalysts, the reclaiming of PGMs from spent catalysts has become essential. Particularly attractive hydrometallurgical methods are those based on the use of halide ions e.g. sodium chloride, as complexing agent in conjunction with nitric acid as oxidant. The chemical reactions between mixtures of aluminium chloride and nitric acid have been studied, but the electrochemical reactions have received little attention. The research reported in this dissertation is aimed at providing data relating to the electrochemical behaviour of platinum in mixtures of aluminium chloride and nitric acid. The construction of Pourbaix diagrams of platinum in chloride environments confirmed that the stable chloro-complexes [PtCl4]2- and PtCl6]2-, as well as platinum oxides (PtO and PtO2) could play a role under the experimental conditions employed in this study. From the thermodynamic results it can be concluded that the systems deserving consideration favour high chloride concentrations and high temperatures. Notable anodic reactions found were the adsorption of chloride on the platinum surface and the gradual formation of [PtCl6]2-, followed by the formation of platinum oxides at 1.00 to 1.01 V. The results show that anodic currents diminished with lower chloride concentrations. A seemingly anomalous anodic behaviour at 35 °C and 45 °C could be explained in terms of a competition between platinum oxide formation and the formation of platinum chloro-complexes. Evidence for the following cathodic reduction reactions was found: hydrogen evolution, reduction of dissolved oxygen to hydrogen dioxide (-1.3 V SHE), nitrate ion reduction to nitrite ions (-0.01 V SHE), nitrite ion reduction to nitric oxide (-0.85 V SHE) and reduction of PtO and PtO2 to Pt (at -1.00 V and 1.01 V SHE, respectively). A brief study was undertaken in an attempt to relate the electrochemical results to the leaching of platinum from a virgin automotive exhaust catalyst. The recovery was low for mixtures with low chloride concentrations, which could be expected from the electrochemical polarisation curves obtained in electrolytes with different chloride concentrations. The maximum platinum recovery attained, was 60% at 45 °C in a mixture containing 0.6 M AlCl3 and 0.9 M HNO3. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

The freezing kinetics of binary nitric acid/water aerosols is of fundamental importance to the modelling of polar stratospheric clouds and the role they in ozone depletion over the Arctic/Antarctic regions. Cirrus clouds are also often composed of nitric acid solutions, hence an understanding of freezing process in these aerosols also aids in modelling the earth's radiation budget and global warming. This thesis explores the kinetic phase diagram of nitric acid/water aerosols with sizes ranging between 0. 2 and 1. 5 mm in radius and concentrations ranging between pure water and 0. 45 mole fraction HNO3. Although the kinetic phase diagram has now been studied between 0. 46 mole fraction HNO3 and pure water, more data is needed in the region between 0. 18 and 0. 25 mole fraction HNO3 to confirm the results reported. The project described in this thesis are a continuation of a project begun by Allan Bertram. The measurements involving aerosols with compositions greater than 0. 25 mole fraction HNO3 were carried out as part of Allan Bertram's Ph. D. thesis (see ref. 20) These data were later examined using a more comprehensive data analysis method (as presented in this thesis) in an effort to obtain a more complete understanding of this system.

Currently in the UK, spent nuclear fuel is reprocessed using the PUREX (Plutonium Uranium Reduction Extraction) process. This process generates large amounts of aqueous nitric acid based waste which is reduced in volume by evaporation before being stored in stainless steel tanks pending eventual disposal to a repository after conversion into a solid wasteform. The corrosivity of nitric acid solutions towards these stainless steel storage tanks is strongly affected by the presence of oxidants that can form in situ if certain dissolved metals such as cerium, chromium, ruthenium and neptunium are present, which is invariably the case in nuclear reprocessing plant liquors. Such liquors are, however, subject to radiolysis leading to the formation of nitrous acid and NOx species in equilibrium with nitric acid and water. The redox chemistry of irradiated reprocessing plant liquors is therefore complex, depending on a large number of factors including acidity, nitrate ion concentration, temperature, pressure, radiation dose rate and the nature/concentration of dissolved species. High acidities, high temperatures and low dose rates favour the oxidation of species such as Ce(III). For example, when Ce(IV) forms, the corrosion rate of stainless steel is strongly increased since the reduction of Ce(IV) forms a kinetically-favoured path way. Furthermore, the presence of nitrous acid (which is radiolytically formed from nitrate/nitric acid) can act to reduce potential corrosion accelerators (e.g. Ce(IV)) to their non-oxidising valency states. These dependencies are only semi-quantitatively understood at present, hampering useful prediction of actual effects when conditions are changed. The research presented within this thesis is divided between two experimental campaigns which are interrelated by their applicability to highly active storage tank conditions; I. An investigation into the conditions which effect the radiolytic production of nitrous acid in nitric acid based solutions was undertaken. This included the quantitative measurement of the steady state concentration of nitrous acid experienced under different conditions. The conditions investigated include temperature, dose rate, gaseous headspace and liquor composition in order to elucidate which factors are of importance in estimating the concentration of nitrous acid which can be expected at the base of a highly active storage tank. The major result of this campaign was that nitrous acid data collected could be used to formulate a g-value of nitrous acid formation (which was found to be 0.71) and this value was used to calculate the nitrous acid production rate expected within a highly active storage tank which is a pre-requisite of underpinning the corrosion chemistry within. II. Investigation into the potential formation of in situ corrosion accelerators in a reprocessing liquor simulant was undertaken. For this, a bespoke experimental rig has been designed, built and operated in order to identify the valency of potential corrosion accelerators at high temperatures while closely representing the conditions expected at the base of a highly active storage tank. This included the simulation of nitric acid radiolysis by means of an appropriate nitrite addition underpinned by the radiolysis studies described above in (I). It was found that none of the conditions investigated were oxidising enough to promote the generation of Ce(IV), which is contrary to the current understanding and should be favourable with regards to the storage tank remnant life expectations. Results reported in this thesis provide insight into the corrosivity of reprocessing liquors under representative storage tank conditions at various temperatures (up to the local liquor saturation temperature) and this knowledge will help improve remnant life predictions of the highly active storage tanks on the Sellafield site.

The large scale nitric acid oxidation of common sugars into their corresponding aldaric acids is being investigated as an important source of potentially useful components for industrial applications such as polymers. This thesis details the development of an Ion Chromatography (IC) method for the analysis of these oxidation mixtures and related samples from the work-up and purification processes. The method was developed for use with a Dionex ICS2000 IC system equipped with an AS11-HC column and utilising suppressed conductivity detection. IC proved to be a useful, versatile and straightforward method of studying the reactions and their products. The detected ions include but are not restricted to the anionic salt forms of: D-Glucaric acid, Xylaric acid, Mannaric acid, D-gluconic acid and both keto forms of the same, D-xylonic acid, D-mannonic acid, glycolic acid, oxalic acid, tartaric acid and tartronic acid. Nitrate from the nitric acid used in the oxidation is often observed. The results compare favorably to GC-MS and HPLC analysis of similar samples. An overview of the theory and operation of the instrument along with the method development and results from application to the oxidation mixtures and related samples are presented. As part of the investigation into the range of utility of IC for studying these reactions, a study was made of the retention behaviour of a large number of simple and low molecular weight (LMW) carboxylic acids eluted by the ion chromatography system in use. The results of this study are included with an explanation of the major factors affecting anion retention on the column

The freezing kinetics of binary nitric acid/water aerosols is of fundamental importance to the modelling of polar stratospheric clouds and the role they in ozone depletion over the Arctic/Antarctic regions. Cirrus clouds are also often composed of nitric acid solutions, hence an understanding of freezing process in these aerosols also aids in modelling the earth's radiation budget and global warming. This thesis explores the kinetic phase diagram of nitric acid/water aerosols with sizes ranging between 0. 2 and 1. 5 mm in radius and concentrations ranging between pure water and 0. 45 mole fraction HNO3. Although the kinetic phase diagram has now been studied between 0. 46 mole fraction HNO3 and pure water, more data is needed in the region between 0. 18 and 0. 25 mole fraction HNO3 to confirm the results reported. The project described in this thesis are a continuation of a project begun by Allan Bertram. The measurements involving aerosols with compositions greater than 0. 25 mole fraction HNO3 were carried out as part of Allan Bertram's Ph. D. thesis (see ref. 20) These data were later examined using a more comprehensive data analysis method (as presented in this thesis) in an effort to obtain a more complete understanding of this system.