Thesis (MScAgric)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: The herbicide atrazine (ATZ, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) has been identified as an environmental endocrine disruptor and possible human carcinogen. The presence of atrazine, along with its degradation products, in soils and water supplies therefore raises concern. Atrazine biodegradation in soils is well-covered to date, however, atrazine degradation by abiotic mineral surfaces, and the chemical mechanism by which it occurs, is not fully understood. Furthermore, with a changing global climate, the effects of wetting and drying cycles on soil processes (e.g. atrazine degradation) is largely unknown, but increasing in importance. This study therefore investigated atrazine degradation on six common soil mineral surfaces, namely birnessite, goethite, ferrihydrite, gibbsite, Al3+-saturated smectite and quartz, as well as the effects that drying these surfaces has on atrazine degradation. In the first part, a comparison was conducted between the reactivity of fully hydrated and drying mineral surfaces toward atrazine, by reacting atrazine-mineral mixtures under both moist and ambient drying conditions, in parallel, for 14 days. Under moist conditions, none of the mineral surfaces degraded atrazine, but under drying, birnessite and goethite degraded atrazine to non-phytotoxic hydroxyatrazine (ATZ-OH, 2-hydroxy-4-ethylamino-6-isopropylamino-1,3,5-triazine) as major product and phytotoxic deethylatrazine (DEA, 2-chloro-4-amino-6-isopropylamino-1,3,5-triazine) as minor product. The mineral surface reactivity was birnessite (66% degradation) > goethite (18% degradation) >> other mineral surfaces (negligible degradation), indicating possible atrazine oxidation. In the second part, the effects of drying rate were investigated on birnessite only (the most reactive surface), by conducting the drying (1) gradually at ambient rates, (2) rapidly under an air stream, and (3) gradually in the absence of water using only organic solvent. After 30 days of ambient drying, 90% of the atrazine was degraded to ATZ-OH and DEA, but the same extent of degradation was achieved after only 4 days of rapid drying with an air stream. Thirty days of gradual drying using only organic solvent did not increase atrazine degradation compared to the water-moist drying surface. In each case, degradation initiated at a critical moisture content of 10% of the original moisture content. In the third part, the degradation mechanism was further investigated. To test for the possible oxidation of atrazine by the birnessite surface, moist atrazine-birnessite mixtures were dried under a nitrogen (N2) stream to eliminate possible oxidation by atmospheric oxygen (O2). Dissolved Mn2+ was extracted at the end of the experiment to observe any reduction of birnessite. Under N2, the same products were formed as before, with no appreciable Mn2+ production, indicating non-oxidative atrazine degradation by birnessite. The final part investigated the effects ultraviolet (UV) radiation has on the degradation of atrazine by drying mineral surfaces. The UV-radiation enhanced the degradation of atrazine, but no other degradation products were formed. It was therefore concluded that atrazine degradation on redox-active soil mineral surfaces is enhanced by drying, via a net non-oxidative mechanism. Furthermore, this drying-induced degradation is an atrazine detoxification mechanism which could be easily applied through agricultural practices such as windrowing, ploughing and any other practice that (rapidly) dries a Mn- or Fe-oxide rich agricultural soil. / AFRIKAANSE OPSOMMING: Die onkruiddoder atrasien (ATS, 2-chloro-4-etielamino-6-isopropielamino-1,3,5-triasien) is as 'n omgewings endokriene versteurder en moontlike menslike karsinogeen geidentifiseer. Die teenwoordigheid van atrasien, tesame met sy afbreekprodukte, in grond en water toevoere wek dus kommer. Die bio-afbreking van atrasien in gronde is tot dusver goed gedek, maar die afbreking van atrasien deur abiotiese mineraaloppervlaktes, en die chemiese meganisme waarmee dit plaasvind, word nie heeltemal verstaan nie. Verder, met 'n veranderende globale klimaat, is die effekte van benatting- en drooging-siklusse op grondprosesse (bv. atrasien afbreking) grootliks onbekend, maar toenemend belangrik. Daarom het hierdie studie atrasien afbreek op ses algemene mineraaloppervlaktes, naamlik birnessiet, goethiet, ferrihidriet, gibbsiet, Al3+-versadigde smektiet en kwarts, ondersoek, asook die effekte wat drooging van hierdie oppervlaktes op atrasien afbreking het. In die eerste deel, was 'n vergelyking gedoen tussen die reaktiwiteit van volgehidreerde en droëende mineraaloppervlaktes teenoor atrasien, deur atrasien-mineraal mengsels, in parallel, onder albei nat en omliggende droogings toestande te reageer vir 14 dae. Onder nat toestande, het geeneen van die mineraaloppervlaktes atrasien afgebreek nie, maar onder drooging het birnessiet en goethiet atrasien afgebreek na nie-fitotoksiese hidroksieatrasien (ATS-OH, 2-hidroksie-4-etielamino-6-isopropielamino-1,3,5-triasien) as hoofproduk en fitotoksiese deetielatrasien (DEA, 2-chloro-4-amino-6-isopropielamino-1,3,5-triasien) as minder-produk. Die mineraaloppervlakte-reaktiwiteit was birnessiet (66% afbreking) > goethiet (18% afbreking) >> ander mineraaloppervlaktes (geringe afbreking), wat moontlike atrasien oksidasie aandui. In die tweede deel, is die effekte van droogingstempo ondersoek, op birnessiet alleenlik (die mees reaktiewe oppervlak) deur drooging by (1) 'n omliggende geleidelike tempo, (2) 'n versnelde tempo onder 'n lugstroom, en (3) 'n geleidelike tempo in die afwesigheid van water, deur slegs gebruik te maak van 'n organiese oplosmiddel. Na 30 dae se geleidelike drooging, is 90% van die atrasien afgebreek na ATS-OH en DEA, maar dieselfe hoeveelheid afbreking is bereik na slegs 4 dae onder versnelde drooging met die lugstroom. Dertig dae van geleidelike drooging met slegs organiese oplosmiddel het nie atrasien afbreking vermeerder in vergelyking met die water-nat droëende oppervlak nie. In elke geval, is afbreking geïnisieer by 'n kritiese water inhoud van 10% van die oorspronklike water inhoud. In die derde deel is die afbrekingsmeganisme verder ondersoek. Om te toets vir die moontlike oksidasie van atrasien deur die birnessiet oppervlak, is nat atrasien-birnessiet mengsels onder stikstof (N2) gedroog, om die moontlike oksidasie deur atmosferiese suurstof (O2) te verhoed. Opgeloste Mn2+ was teen die einde van die eksperiment geekstraëer om enige reduksie van birnessiet waar te neem. Onder N2 is dieselfde produkte as voorheen gevorm, met geen aansienlike Mn2+ produksie nie, aanduidend van 'n nie-oksideerende afbreek van atrasien deur birnessiet. Die laaste deel het die effekte van ultraviolet (UV) straling op die afbreek van atrasien op droëende mineraaloppervlaktes ondersoek. Die UV-straling het atrasien afbreek vermeerder, maar geen ander afbreek-produkte is gevorm nie. Die gevolgtrekking is dus dat atrasien afbreking op redoks-aktiewe mineraal-oppervlaktes verhoog word met drooging, deur 'n netto nie-oksidasie meganisme. Verder is hierdie drooging-geinduseerde afbreking 'n atrasien ontgiftingsmeganisme wat eenvoudig toegepas kan word deur landboupraktyke soos windrying, ploeg en ander praktyke wat (vinnig) 'n Mn- of Fe-oksied ryke landbou grond verdroog. / National Research Foundation (NRF)

Thesis (Ph.D (Physics)) --University of Limpopo, 2005 / We have derived a potential model for °uorapatite Ca10(PO4)6F2, ¯tted to structure, elastic constants and vibrational frequencies of the phosphate groups, which is compatible with existing calcite and °uorite potential mod- els. We then modelled the structure and stabilities of the dry and hydrated f0 0 0 1g, f1 0 1 0g, f1 0 1 1g, f1 1 2 0g, f1 0 1 3g and f1 1 2 1g surfaces, which calculations con¯rmed the experimental dominance of the f0 0 0 1g surface, which is prominently expressed in the calculated thermodynamic morphologies. The dehydrated morphology further shows the experimental f1 1 2 1g twinning plane, while the f1 0 1 0g cleavage plane is expressed in the hydrated morphology. Molecular adsorption of water has a stabilising e®ect on all six surfaces, where the surfaces generally show Langmuir be- haviour and the calculated hydration energies indicate physisorption (73 - 88 kJ mol¡1). The chains of °uoride ions surrounded by hexagonal calcium channels can become distorted in two major ways during relaxation: either by a shortening/lengthening of the FF distances, when the channel is perpendicular to the surface, or by distortion of the CaF bonds when the channel is parallel to the surface. Both distortions occur when the channel runs at an angle to the surface. Other relaxations include compression of the calcium sub-lattice and rotation of surface phosphate groups. We have modelled adsorption of a range of organic molecules onto dif- ferent °uorapatite surfaces, due to the importance of organic/ inorganic in- teractions in biological situations. We have selected organic molecules that represent a model for the carboxylic acids, alkyl hydroxamates and those 3 that contain both the aldehyde and hydroxyl functional groups. Adhesion of these organic molecules on the surfaces has shown strong interaction between the surface's Ca ions and the molecule's oxygens, more especially the car- bonyl oxygens than any other interactions. It was found that the number of interactions between the ions of adsorbate molecule and the mineral surfaces thus contribute signi¯cantly to the exothemicity of adsorption. Further more, simulations of apatite thin ¯lms at a range of ®-quartz surfaces have shown how the strength of adhesion between thin ¯lms of ap- atite material and ceramic silica surfaces is crucially dependent upon both the orientation of the ¯lm relative to the substrate and the nature of the silica surfaces, a ¯nding that is important in a wide number of applications, from basic geological research on intergrowth of phosphate and silicate rock minerals to the search for more e®ective surgical implant materials. It was shown that although the unrelaxed quartz surface is more reactive toward the apatite ¯lm, the more regular thin ¯lm structures grown at the pre-relaxed quartz surfaces lead to more stable interfaces. Film growth at the unrelaxed quartz surface is energetically increasingly unfavorable, whereas growth at the pre-relaxed surface is calculated to continue beyond the ¯rst layer, where the adhesion energy is convergent with the layer growth of the thin ¯lm. Ad- hesion of apatite thin ¯lm on hydroxylated surfaces of ®-quartz has shown to be energetically less favourable than at dry surfaces. This was because the thin ¯lm interact mainly with the hydroxyl ions on the surface of quartz. However, the adhesion energy is still convergent with layer growth of the thin ¯lm on the hydroxylated surfaces. / National Research Foundation of South Africa (NRF), Council for Scientific and Industrial research (CSIR), and the University of the North

xvii, 209 p. : ill. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Altering and controlling the properties of solid surfaces in aqueous or other liquid phase environments has been a sought after objective for decades. With the discovery of chemisorbed self-assembled monolayers, this dream has become a reality. Oxide and metal surfaces can now be readily coated with an array of commercially available products to produce a desired fnctionality. The presence of these coatings on solid surfaces affects properties of the interfacial region by altering interfacial electrostatic fields, changing the structure of interfacial water molecules and altering the interactions of adsorbed species. This dissertation reports on in situ studies of adsorption at several solid/aqueous interfaces using vibrational sum-frequency spectroscopy, a surface specific technique. These studies are augmented by the use of atomic force microscopy and contact angle goniometry to characterize the prepared surfaces and their interactions with adsorbates. The studies investigate how changes in the surface structure and chemistry, as well as the bulk aqueous phase, affect interfacial structure. The studies within are primarily focused on the interactions of water with bare and functionalized fused silica and the relationship between the aqueous phase composition and the structure of fluorocarbon and hydrocarbon self-assembled monolayers. The variations in aqueous structure are then examined in detail using ionic strength controlled experiments to understand the direct interactions of water hydrophobically coated silica. This analysis is followed by an investigation of the competitive adsorption of methanol and water at fluorocarbon and hydrocarbon monolayers which show spectroscopic signatures of the interaction strength between fluorocarbons and hydrocarbons. Further studies are performed using butylammonium chloride to verify these spectroscopic signatures and reveal different molecular structures of adsorbed species at chemically different hydrophobic surfaces. Lastly, specific ion effects on the CaF 2 /water interface are shown using equilibrium and time-resolved sum-frequency spectroscopy. The results of all these studies have implications for an array of surface chemical applications from mineral flotation to biocompatibility. This dissertation includes previously published co-authored material. / Committee in charge: Thomas Dyke, Chairperson, Chemistry; Geraldine Richmond, Advisor, Chemistry; James Hutchison, Member, Chemistry; Mark Lonergan, Member, Chemistry; Qusheng Jin, Outside Member, Geological Sciences

La compréhension des cycles couplés de la matière organique et des éléments traces métalliques (ETMs) tels que Cu, Zn, Cd, Pb et les lanthanides (Ln) dans les sols nécessite des connaissances sur les espèces formées aux interfaces solide-solution. La sorption des acides fulviques (AFs) sur les surfaces minérales est d’importance car les AFs modifient la réactivité de surface et la capacité de sorption des minéraux vis-à-vis des ETMs. Les AFs sont des mélanges complexes de milliers de composés organiques qui subissent un fractionnement chimique lors de leur sorption sur les surfaces minérales des sols. Le but principal de cette étude est d’élucider le fractionnement d’AFs d’origines et de compositions différentes sur des surfaces minérales (argiles, hydroxydes de fer et d’aluminium) d’intérêt pour les sols, et d’en investiguer l’effet sur la sorption des ETMs dans des systèmes métaux-AF-minéral-solution modèles. Il s’agit ensuite d’appliquer les connaissances acquises dans les systèmes modèles à la compréhension du comportement des ETMs dans des systèmes eaux-sols.L’utilisation de la spectrométrie de masse haute résolution ESI(-)-FTMS pour l’analyse de solution d’AFs (PPH,extrait d’un sol sous hêtraie ; PPC, extrait d’un sol sous conifères; PPFA, AF de référence issu d’une tourbe)issus d’expériences de sorption sur l’hématite, l’alumine et la kaolinite a permis de mettre en évidence que les propriétés de surface des minéraux sont un paramètre clé régissant le fractionnement de sorption des AFs. Les données ont montré que l'affinité relative des molécules d’un AF pour la surface des oxydes métalliques est régie par l'acidité moléculaire, l’échange de ligand étant le principal mécanisme impliqué dans le processus de sorption à pH acide. En revanche, la surface de la kaolinite a montré une faible sélectivité, la sorption résultant principalement de la formation de liaisons H avec les sites de faible affinité sur les plans basaux des particules.En combinant des données macroscopiques sur la sorption compétitive des métaux (Cu, Zn, Cd, Pb et Ln) avec des descriptions à l'échelle moléculaire du fractionnement de PPH sur l’hématite et la kaolinite à différents rapports AF/minéraux, nous avons mis en évidence que le comportement de sorption des métaux sur une surface minérale en présence d’AFs est largement influencé par la distribution moléculaire des AFs aux interfaces minéral-solution, qui dépend principalement de la nature (oxyde métallique versus argile) et des propriétés des surfaces minérales ainsi que du rapport AF/minéral dans le cas des oxydes métalliques.L’acquisition de données sur deux profils de sols développés sous hêtraie et sous conifères par différentes approches complémentaires (minéralogie, calculs de bilans massiques, extractions séquentielles, et analyses ESI(-)-FTMS des substances humiques) a montré que les dynamiques (distribution verticale, fractionnement) des AFs et le comportement des ETMs sont interconnectés et gouvernés par la nature et la réactivité des surfaces minérales présentes dans les sols. / Building a comprehensive description of the coupled cycles of organic matter and trace metal elements (TMEs) such as Cu, Zn, Cd, Pb and lanthanides (Ln) in soils requires knowledge on the species formed at the solid-solution interfaces. The sorption of fulvic acids (FAs) on mineral surfaces is of importance, because FAs modify the surface reactivity and the sorption capacity of minerals towards TMEs. FAs are complex mixtures of thousands of organic compounds which undergo a chemical fractionation during their sorption on mineral surfaces of soils. The purpose of this study was to elucidate the fractionation of FAs of different origins and compositions on mineral surfaces (Fe and Al hydroxides, clays) relevant to soils, and to investigate its effect on the sorption of TMEs in model metals-FA-mineral-solution systems. The next step was to use the knowledge acquired on model systems for understanding the behavior of TMEs in water-soil systems. The use of high-resolution ESI(-)-FTMS mass spectrometry for analyzing FA solutions (as FAs: PPH, extracted from a soil under a beech forest; PPC, extracted from a soil under a fir forest; and PPFA, a reference peat FA) resulting from sorption experiments onto hematite, alumina and kaolinite provided evidence that mineral surface properties are a key parameter governing the FA sorptive fractionation. The MS data showed that the relative affinity of FA molecules for the surface of metal oxides is governed by molecular acidity, ligand exchange being the main mechanism involved in the sorption process at acidic pH. In contrast, the surface of kaolinite displayed alow selectivity, the sorption resulting mainly from H-bonding with low-affinity basal sites. By combining macroscopic data on the competitive sorption of metals (Cu, Zn, Cd, Pb and Ln) with molecular scale descriptions of PPH fractionation onto hematite and kaolinite at different FA/mineral ratios, we have shown that the sorption behavior of metals on mineral surfaces in the presence of PPH is greatly impacted by the molecular distribution of PPH at the mineral-solution interface, which mainly depends on the nature (metal oxidevs clay) and properties of the mineral surfaces as well as on the FA/mineral ratio for metal oxides. Data acquired on two soil profiles developed under beech and fir forests by using different complementary approaches (mineralogy, mass balance calculations, sequential extractions and ESI(-)-FTMS analyzes of humic substances) showed that the dynamics (vertical distribution, fractionation) of FAs and the behavior of TMEs are interconnected and governed by the nature and reactivity of mineral surfaces in soils.

Humic acids and humates are principal components of humic substances major organic constituents of soil, peat, coal and water around the world. I was involved in research into molecular dynamics simulations of interactions of quartz surfaces with aqueous solutions of ions and small organic molecules representing basic building blocks of larger biomolecules and functional groups of organic matter. We studied interactions of molecules with surfaces for a set of surface charge densities corresponding to the experimentally or environmentally relevant ranges of pH values employing molecular mechanics, molecular dynamics and ab initio techniques. Simulated quartz surfaces covered the range of surface charge densities 0.00, -0.03, -0.06 and -0.12 C-m-2, approximately corresponding to pH values 4.5, 7.5, 9.5 and 11. As model molecules, benzoic acid, phenol, o-salicylic acid and their conjugated bases were chosen. My task was to prepare topologies and parametric models of selected organic matter basic building blocks organic molecules. I focused on studying interactions of these molecules in an aqueous environment with mineral surface quartz. The aim was to process simulation results and analyse conformations of the adsorption complexes and their thermodynamic properties such as interaction energies, free energies and adsorption geometries.