The atmosphere is a heterogeneous system which is rich in potential chemistry. The processes taking place within this system as well as at the interface of its constituents are of immense importance in understanding how the atmosphere in turn can impact the well-being of all living on the surface of earth. Thus, the heterogeneous chemistry of atmospheric aerosols has since long been subjected to extensive scientific investigation, in view of broadening our understanding of this imperative system. In this study, the heterogeneous interactions of water vapor and gaseous HNO3 on goethite (a-FeOOH), a prominent component of mineral dust aerosol is investigated with quartz crystal microbalance (QCM) measurements and attenuated total reflectance - Fourier transform IR (ATR-FTIR) spectroscopy. Laboratory synthesized goethite samples of varying size (microrods of specific surface area 34 m2/g and nanorods of specific surface area 121 m2/g) were used in order to identify the size dependent interaction of goethite with H2O and HNO3. The study revealed that the exposure of goethite to gas phase H2O and HNO3 results in the uptake of these gases via surface adsorption. Additionally, this novel combined approach of QCM and ATR-FTIR spectroscopy allowed for quantification of the amount of uptake while the spectroscopic data provided information on the speciation of adsorbed products. Thus, with the QCM and spectroscopic data in hand, a precise interpretation of the reactivity as well as its size dependence was sought. In a general sense, the reactivity of a substance is believed to increase with decreasing particle size. The results of this investigation show that in the case of H2O, both microrods and nanorods take up water while the total amount of adsorbed water, when normalized to surface area, is similar for both particle sizes. However, for HNO3, the saturation coverage of total and irreversibly bound HNO3 on microrods was observed to be higher than that on nanorods. With supplementary analysis, this anomalous size effect was attributed to structural features such as the involvement of surface hydroxyl groups in determining the reactivity, which would be subjected to change as a function of particle size. Furthermore, an investigation of the behavior of HNO3 reacted goethite in aqueous media and the uptake of H2O and HNO3 at their mutual presence was carried out such as to better understand the effects of atmospheric processing upon dispersal within the hydrosphere. Further analysis is warranted before arriving at a general conclusion on the size-dependent reactivity of goethite. However, we may argue that goethite containing aerosols may indicate the same pattern of reactivity within the atmosphere as that observed here. Thus, the inference of this investigation proves to be significant in broadening our understanding of this atmosphere as well as the entire biosphere as a whole.

Iron oxides, have been widely studied as promising anode materials in lithium-ion batteries (LIBs) for their high capacity (≈ 1000 mA h g-1 for Fe2O3 and Fe3O4,), non-toxicity, and low cost. In this work, β-FeOOH has been evaluated within a LIB half-cell showing an excellent capacity of ≈ 1500 mA h g-1 , superior to Fe2O3 or Fe3O4. Reaction mechanism has been proposed with the assistance of X-ray photoelectron spectroscopy (XPS). Various magnetic properties have been suggested for β-FeOOH such as superparamagnetism, antiferromagnetism and complex magnetism, for which, size of the material is believed to play a critical role. Here, we present a size-controlled synthesis of β-FeOOH nanorods. Co-existing superparamagnetism and antiferromagnetism have been revealed in β-FeOOH by using a Physical Property Measurement System (PPMS). Compared with the high price of lithium in LIBs, sodium-ion batteries (SIBs) have attracted increasing attentions for lower cost. Recent studies have reported Na0.44MnO2 to be a promising candidate for cathode material of SIBs. This thesis has approached a novel solid-state synthesis of Na0.44MnO2 whiskers and a nano-scaled open cell for in situ TEM study. Preliminary results show the first-stage fabrication of the cell on a biasing protochip.

L'arsenic est un metalloïde toxique et cancérigène. Ubiquiste dans la pedosphere, il est très sensibleaux fluctuations des conditions redox du sol, ce qui influe significativement sa toxicité et mobilité. Nousétudions le cycle biogéochimique global de l'arsenic, en tenant compte de l'usage croissant des ressources, etpassons en revue l'importance respective de l’arsenic geogénique et anthropogénique dans l’environnement.La contamination à l’arsenic est souvent diffuse dans les bassins sédimentaires de l'Europe. Cependant, desconcentrations dans l'eau interstitielle du sol peuvent être élevées lors de périodes de saturation du solcausées par la monté des eaux souterraines ou les inondations, prévues d'augmenter dû aux changementsclimatiques. La spectrométrie de fluorescence X quantitative et sans standard a été utilisée pour analyserl'arsenic dans des sols relativement contaminés de la plaine alluviale de la Saône au moyen de protocoles depréparation d'échantillons conçus pour optimiser la précision d'analyse et l'exactitude in situ aux bassesconcentrations d'arsenic. L'arsenic dans ces sols est associe aux (hydr)oxydes du fer et de manganèse de lataille d'argile colloïdale. Ceux-ci subissent une dissolution réductrice par les microorganismes lors desinondations, libérant une importante concentration d'arsenic dans la phase aqueuse. Si, par la suite, l'arsenicdégagé n'est pas éliminé avec l'eau de crue évacuée, il est ré-immobilisé pendant l'oxydation du sol et lareprécipitation des oxydes métalliques. Grâce à une combinaison novatrice d'analyses chimiques par voiehumide, d’écologie microbienne, de spectroscopie ainsi que de modélisation thermodynamique et cinétique,nous démontrons que les cycles d'oxydo-réduction séquentiels entraînent une atténuation d'arsenic aqueuxdans des conditions réductrices dû à la coprécipitation croissante, et a une diminution de l'activitémicrobienne causée par l’appauvrissement en matière organique labile. Des processus d'atténuationsimilaires sont observés en l'absence d'activité microbienne pour Cr et As dans des argiles pyriteuses lorsquecelles-ci sont exposés aux oscillations redox provoquées par l'ajout de substances humiques réduites. Ainsi,nous montrons que les effets cumulatifs de cycles redox successifs sont extrêmement importants pour lamobilité de divers contaminants dans l'environnement. / Arsenic is a toxic and carcinogenic metalloid, ubiquitous in the pedosphere and highly sensitive tofluctuations in soil redox conditions which dramatically influence both its toxicity and mobility. We reviewthe global biogeochemical cycle of arsenic in light of increasing resource usage and re-evaluate theimportance of anthropogenic and geogenic arsenic inputs to the exogenic cycle. Arsenic contamination isoften diffuse in European sedimentary basins. Despite this, concentrations in soil pore-water may be highduring periods of soil saturation caused by rising groundwater or surface flooding which is predicted toincrease due to climatic change. Standardless quantitative X-ray fluorescence spectrometry is used toanalyse for arsenic in moderately contaminated soils on the alluvial plain of the Saône River with samplepreparation protocols designed to optimize analytical precision and accuracy in-situ at trace arsenicconcentrations. Arsenic in these soils is shown to be associated with colloidal and clay sized iron andmanganese (hydr)oxides which undergo microbially mediated reductive dissolution during flooding, releasingsubstantial arsenic to the aqueous phase. If released arsenic is not subsequently removed with recedingflood water it is re-immobilized during soil oxidation and re-precipitation of metal oxides. We demonstratethrough a novel combination of wet chemistry, microbial ecology, spectroscopy and thermodynamic andkinetic modelling that sequential reduction-oxidation cycles result in aqueous arsenic attenuation duringreducing conditions due to increased co-precipitation and decreases in microbial activity due to depletion oflabile organic matter. Similar attenuation processes are observed in the absence of microbial activity for Crand As in pyrite-bearing clays when subjected to redox oscillations induced by addition of reduced humicsubstances. We demonstrate that the cumulative effects of successive redox cycling are therefore of greatimportance to contaminant mobility in a variety of environments. / El arsénico es un metaloide tóxico y cancerígeno, ubicuo en la pedosfera y altamente sensible a lasfluctuaciones de las condiciones redox del suelo, las cuales controlan tanto su toxicidad como su movilidad.La presente tesis doctoral tiene como objeto de estudio el ciclo biogeoquímico global del arsénico y examinala importancia de los aportes del arsénico antropogénicos y geogénicos al ciclo exógeno tomando en cuentael uso creciente de recursos.La contaminación con arsénico es generalmente difusa en las cuencas sedimentarias europeas. No obstante,las concentraciones en las aguas intersticiales del suelo pueden ser elevadas durante los periodos desaturación causados por el aumento de aguas subterráneas o inundaciones, cuyo incremento se prevédebido a los cambios climáticos. La espectrometría de fluorescencia de Rayos-X cuantitativa y sin estándar esutilizada para analizar el arsénico en suelos relativamente contaminados en la llanura aluvial del río Saône,mediante protocolos de preparación de muestras diseñados para mejorar la precisión analítica y la exactitudin-situ a bajas concentraciones de arsénico. La presencia de arsénico en estos suelos demuestra estarasociada a los (hidr)óxidos de hierro y de manganeso de tamaño de arcilla coloidal, los cuales experimentanuna disolución reductora por acción microbiana durante las inundaciones, liberando así una importanteconcentración de arsénico en la fase acuosa. Si, posteriormente, el arsénico despedido no se elimina con elagua saliente, éste se vuelve a inmovilizar durante la oxidación del suelo y la re-precipitación de óxidosmetálicos. Gracias a una combinación innovadora de análisis químicos por vía húmeda, ecología microbiana,espectroscopia, así como modelado termodinámico y cinético, demostramos que los ciclos de oxidoreducciónsecuenciales provocan una atenuación de arsénico acuoso durante condiciones de reduccióndebido al aumento de coprecipitacion y disminución de la actividad microbiana causada por el agotamientode materia orgánica lábil. Se observan procesos de atenuación similares en caso de ausencia de actividadmicrobiana para Cr y As en arcillas piritas cuando son sometidos a oscilaciones de redox inducidas mediantela adición de sustancias húmicas reducidas. Es así como demostramos que los efectos acumulativos de ciclossucesivos de redox son muy importantes para la movilidad contaminante en una variedad de ambientes.

No / The Sikhote-Alin (SA) meteorite is an example of a type IIAB octahedrite iron meteorite with ca. 0.5 wt% phosphorus (P) content principally in the form of the siderophilic mineral schreibersite (Fe,Ni)(3)P. Meteoritic in-fall to the early Earth would have added significantly to the inventory of such siderophilic P. Subsequent anaerobic corrosion in the presence of a suitable electrolyte would produce P in a form different to that normally found within endogenous geochemistry which could then be released into the environment. One environment of specific interest includes the low pH conditions found in fumaroles or volcanically heated geothermal waters in which anodic oxidation of Fe metal to ferrous (Fe2+) and ferric (Fe3+) would be coupled with cathodic reduction of a suitable electron acceptor. In the absence of aerobic dioxygen (E-o = +1.229 V), the proton would provide an effective final electron acceptor, being converted to dihydrogen gas (E-o = 0 V). Here we explore the hydrothermal modification of sectioned samples of the Sikhote-Alin meteorite in which siderophilic P-phases are exposed. We report on both, (i) simulated volcanic conditions using low pH distilled water and (ii) geothermally heated sub-glacial fluids from the northern Kverkfjoll volcanic region of the Icelandic Vatnajokull glacier. A combination of X-ray photoelectron spectroscopy (XPS) and electrochemical measurements using the scanning Kelvin probe (SKP) method reveals that schreibersite inclusions are significantly less susceptible to anodic oxidation than their surrounding Fe-Ni matrix, being some 550 mV nobler than matrix material. This results in preferential corrosion of the matrix at the matrix-inclusion boundary as confirmed using topological mapping via infinite focus microscopy and chemical mapping through Raman spectroscopy. The significance of these observations from a chemical perspective is that electrochemically noble inclusions such as schreibersite are likely to have been released into the geological environment through an undermining corrosion of the surrounding matrix, thus affording localised sources of available water-soluble, chemically reactive P in the form of H-phosphite [H2PO3-, Pi(III) as determined by P-31 NMR spectroscopy]. This compound has been shown to have considerable prebiotic chemical potential as a source of condensed P-oxyacids. Here we demonstrate that Pi(III) resulting from the hydrothermal modification of Sikhote- Alin by sub-glacial geothermal fluids can be readily dehydrated into the condensed P-oxyacid pyrophosphite [H2P2O52-, PPi(III)] by dry-heating under mild (85 degrees C) conditions. The potential significance of this latter condensed P-compound for prebiotic chemistry is discussed in the light of its modified chemical properties compared to pyrophosphate [H2P2O72-, PPi(V)].

L'arsenic est un metalloïde toxique et cancérigène. Ubiquiste dans la pedosphere, il est très sensibleaux fluctuations des conditions redox du sol, ce qui influe significativement sa toxicité et mobilité. Nousétudions le cycle biogéochimique global de l'arsenic, en tenant compte de l'usage croissant des ressources, etpassons en revue l'importance respective de l'arsenic geogénique et anthropogénique dans l'environnement.La contamination à l'arsenic est souvent diffuse dans les bassins sédimentaires de l'Europe. Cependant, desconcentrations dans l'eau interstitielle du sol peuvent être élevées lors de périodes de saturation du solcausées par la monté des eaux souterraines ou les inondations, prévues d'augmenter dû aux changementsclimatiques. La spectrométrie de fluorescence X quantitative et sans standard a été utilisée pour analyserl'arsenic dans des sols relativement contaminés de la plaine alluviale de la Saône au moyen de protocoles depréparation d'échantillons conçus pour optimiser la précision d'analyse et l'exactitude in situ aux bassesconcentrations d'arsenic. L'arsenic dans ces sols est associe aux (hydr)oxydes du fer et de manganèse de lataille d'argile colloïdale. Ceux-ci subissent une dissolution réductrice par les microorganismes lors desinondations, libérant une importante concentration d'arsenic dans la phase aqueuse. Si, par la suite, l'arsenicdégagé n'est pas éliminé avec l'eau de crue évacuée, il est ré-immobilisé pendant l'oxydation du sol et lareprécipitation des oxydes métalliques. Grâce à une combinaison novatrice d'analyses chimiques par voiehumide, d'écologie microbienne, de spectroscopie ainsi que de modélisation thermodynamique et cinétique,nous démontrons que les cycles d'oxydo-réduction séquentiels entraînent une atténuation d'arsenic aqueuxdans des conditions réductrices dû à la coprécipitation croissante, et a une diminution de l'activitémicrobienne causée par l'appauvrissement en matière organique labile. Des processus d'atténuationsimilaires sont observés en l'absence d'activité microbienne pour Cr et As dans des argiles pyriteuses lorsquecelles-ci sont exposés aux oscillations redox provoquées par l'ajout de substances humiques réduites. Ainsi,nous montrons que les effets cumulatifs de cycles redox successifs sont extrêmement importants pour lamobilité de divers contaminants dans l'environnement.

Thesis submitted in fulfilment of the requirements for the degree DOCTOR TECHNOLOGIAE: ENGINEERING: CHEMICAL in the FACULTY OF ENGINEERING at the CAPE PENINSULA UNIVERSITY OF TECHNOLOGY 2014 / Several authors have reported on the use of alcohols – water /or mixed solvents to synthesise metal oxide nanoparticles. However, no systematic study has been carried out to evaluate the effect of mixed solvent on the particle characteristics, although considerable research has been reported, a gap still exists with regard to the effect of the alcohols as solvents on the growth kinetics of nanoparticles. To address these issues, four different alcohols, namely, methanol (MeOH), ethanol (EtOH), propanol (PrOH) and butanol (BuOH) were used as solvents in the synthesis of β-FeOOH particles. The effect of organic solvents on the growth kinetics of β-FeOOH nanorods has been evaluated for the first time in this study. Two-stage growth of akaganeite nanorods has been observed in BuOH and PrOH. The first growth stage follows a typical power law representing Ostwald ripening (OR) kinetic. The second stage was found to be asymptotic and obeyed oriented attachment (OA) kinetic. The proof of the OA kinetic also comes from the HRTEM images of the synthesised particles. Simultaneous occurrence of the two mechanisms was observed in the growth of the particles synthesised in EtOH and MeOH. The rate constants for OR kinetic, KOR, was found to be higher than the rate constant for OA kinetic, KOA, for different solvents used. Preamble The use of a mixed solvent is a new approach in the synthesis and processing of materials. Various researchers have stated that the surface tension of the solvent plays an important role in the formation of uniform nanorods. However, the effect of surface tension was not correlated with the particle growth, earlier, though the dielectric properties of the mixed solvents were only taken into account. Additionally, no quantitative or qualitative relationship was presented between surface tension and particle growth in the literature. In this work an attempt to correlate these two parameters (surface tension and particle growth) with the concentration of the precursor and temperature was made, resulting in an exponential relationship between KOR for the particle growth and surface tension of the alcohols. Furthermore, the relationship between surface tension and particle growth was validated by an independent study using statistically designed experiments to account for the influence of various process variables on the particle growth. The findings in this study obtained from both theoretical and experimental work provides an insight into the relationship between solvent surface tension and particle growth interactions, producing a new piece of information that will further promote our understanding of the formation mechanisms of β- FeOOH growth. The transformation temperature of akaganeite (β-FeOOH) nanorods to hematite (α-Fe2O3) particles was found to be solvent dependent. Thermogravimetric analysis and differential scanning calorimetry were performed to evaluate the effect of alcohol on the thermodynamic stability of the particles. Alcohol as solvent played a significant role in the dehydration property of the synthesised particles. The percentage mass loss of the particles at 300°C decreases linearly with increasing carbon number in the linear alkyl chain of the solvent. The effect of alcohol type on the particle morphology was found to be more pronounced at higher FeCl3 concentrations (>0.5M). Splitting of β-FeOOH nanorods was observed at FeCl3 concentration of 0.7M in BuOH. In PrOH, rectangular morphologies were obtained whereas nanoribbons resulted in surfactant-free conditions. It was found that the nature of anions (chloride vs. nitrate and sulphate) in the precursor salt also influenced the morphology.