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This dissertation includes theoretical and applied components that address the effect of coatings on rates of mineral reactions that occur in acid mine drainage (AMD) environments. The two major projects investigated how diffusion-limited transport of reactants through pore spaces in coatings on mineral grains affects the reaction rate of the underlying mineral. The first project considered the growth of gypsum coatings on the surface of dissolving limestone in anoxic limestone drains (ALD), which reduces the neutralization rate of the dissolving limestone and the subsequent effectiveness of this treatment. The second project investigated the conditions where iron oxyhydroxide coatings form on oxidizing pyrite and the potential strategies to prevent "runaway" AMD by reducing the rate of acid production to the point that the acid can be neutralized by the surrounding rocks. In both studies, experiments were conducted to measure reaction rates for the underlying minerals, as coatings grew thicker. These experimental data were fit to a diffusion model to estimate diffusion coefficients of reactants through pore spaces in coatings. These models are extrapolated to longer times to predict the behavior of the coated grains under field conditions. The experimental results indicate that management practices can be improved for ALDs and mine waste piles. For example, supersaturation with respect to gypsum, leading to coating formation, can be avoided by diluting the ALD feed solution or by replacing limestone with dolomite. AMD can be prevented if the rate of alkalinity addition to mine waste piles is faster than acid is produced by pyrite oxidation. The diffusion model developed in this study predicts when iron oxyhydroxide coatings will become thick enough that alkalinity from the surroundings is sufficient to neutralize acid produced by coated pyrite oxidation and additional alkalinity is no longer required. / Ph. D.

Environmental contamination issues related to phosphorus (P) in surface waters substantiates the need to identify minimally-sufficient P fertilization amounts for production of containerized nursery crops and better understand the effect of routine amendments (i.e., dolomite [DL] and micronutrient fertilizer [MF]) added to pine bark substrates on chemical fate of P fertilizer. Four studies were conducted to accomplish two overarching objectives: 1) determine the minimum P fertilization amount and corresponding pore-water P concentration needed to achieve maximal growth of common containerized nursery crops and 2) determine the effect of DL and MF amendments in pine bark on P retention during irrigation and P fractions in substrate pore-water. In a fertigation, greenhouse study, calculated lowest P-fertilizer concentration that sustained maximal growth in Hydrangea paniculata ‘Limelight’ (panicle hydrangea) and Rhododendron ‘Karen’ (azalea) was 4.7 and 2.9 mg·L⁻¹ , respectively, and shoot growth Ilex crenata ‘Helleri’ (holly) was the same when fertilized with 0.5 to 6.0 mg·L⁻¹ P. Porewater P concentrations corresponding with treatments that sustained maximal growth of panicle hydrangea, azalea and holly were as low as 0.6, 2.2 and 0.08 mg·L⁻¹ P, respectively. In a separate study, utilizing low-P controlled-release fertilizers (CRFs), shoot growth of Hydrangea macrophylla ‘P11HM-11’ (bigleaf hydrangea) produced in two ecoregions was maximal when fertilized with as little as 0.3 g CRF-P per 3.8-L container, a 50% P reduction from the industrystandard CRF. Holly required 0.2 or 0.4 g CRF-P depending on ecoregion. Mean pore-water P concentrations that corresponded with highest SDW were 0.8 and 1.2 mg·L⁻¹ for hydrangea and holly, respectively. When irrigating fallow pine bark columns containing CRF for 48 d, amending pine bark with DL and MF reduced orthophosphate-P (OP-P) leachate concentrations by ≈ 70%, most of which was retained within the substrate. In a greenhouse study, containerized Lagerstroemia ‘Natchez’ (crape myrtle) were grown for 91 d in pine bark containing CRF. In pine bark amended with DL and MF, pore-water OP-P and total P concentrations, measured approximately weekly, were reduced by, on average, 64% and 58%, respectively. Total dry weight values of plants grown with DL plus MF or MF-only were 40% higher than those grown with no amendments; however, tissue P amounts and relative P uptake efficiency were the same among plants in these three treatments. Therefore, sorption of OP-P by DL and MF reduced water-extractable OP-P but did not limit P uptake by plants. / Ph. D.

The Chatham Islands are located in the SW Pacific Ocean, approximately 850 km to the east of the South Island of New Zealand. This small group of islands is situated near the eastern margin of the Chatham Rise, an elongated section of submerged continental crust that represents part of the Late Paleozoic-Mesozoic Gondwana accretionary margin. The location and much of the geology of the Chatham Islands are attributed to intra-plate basaltic volcanism, initiated during the Late Cretaceous, in association with development of a failed rifting system to the south of the Chatham Rise. Despite the volcanic nature of much of the geology, the majority of the Cenozoic sedimentary stratigraphic record on the islands comprises non-tropical skeletal carbonate deposits whose deposition was often coeval with submarine volcanics and volcaniclastic deposits. This has resulted in complex stratigraphic relationships, with the volcanic geology exerting a strong influence on the geometry and distribution of the carbonate deposits. These limestones, despite some general field descriptions, have been little studied and are especially poorly understood from a petrographic and diagenetic perspective. The carbonate geology in detail comprises eleven discrete limestone units of Late Cretaceous through to Pleistocene age which were studied during two consecutive field expeditions over the summers of 2005 and 2006. These limestone occurrences are best exposed in scattered coastal outcrops where they form prominent rugged bluffs. While many of the younger (Oligocene to Pliocene) outcrops comprise of poorly exposed, thin and eroded limestone remnants (it;5 m thick), older (Late Paleocene to Early Oligocene) exposures can be up to 100 m in thickness. The character of these limestones is highly variable. In outcrop they display a broad range of textures and skeletal compositions, often exhibit cross-bedding, display differing degrees of porosity occlusion by cementation, and may include rare silicified horizons and evidence of hardground formation. Petrographically the limestones are skeletal grainstones and packstones with a typical compositional makeup of about 70% skeletal material, 10% siliciclasts, and 20% cement/matrix. Localised increases in siliciclastics occur where the carbonates are diluted by locally-derived volcaniclastics. The spectrum of skeletal assemblages identified within the Chatham Island limestones is diverse and appears in many cases to be comparable to the bryozoan dominant types common in mainland New Zealand and mid-latitude Australian cool-water carbonates in general. However, some key departures from the expected cool-water carbonate skeletal makeup have been identified in this study. The occurrence of stromatolitic algal mats in Late Cretaceous and Early Eocene carbonate deposits indicates not cool-temperate, but certainly warm-temperate paleoclimatic conditions. A change to cool-temperate conditions is recorded in the limestone flora/fauna from the mid-Late Miocene times following the development and later northward movement of the Subtropical Front. An uncharacteristic mix of shallow-shelf (bryozoans) and deeper water fauna (planktic foraminifera), together with their highly fragmented and abraded nature, is indicative of the likely remobilisation and redistribution of carbonate, primarily during episodic storm events. The Chatham Islands limestones formed within the relative tectonic stability of an oceanic island setting, which was conducive to ongoing carbonate accumulation throughout much of the Cenozoic. This contrasts markedly with other mainland New Zealand shelf carbonates which formed over sporadic and short-lived geological periods, experiencing greater degrees of burial cementation controlled by a relatively more active tectonic setting. As a consequence of the tectonically stable setting, the Chatham Islands limestones have experienced little burial and exhibit a paucity of burial cementation effects. They remain commonly soft and friable. Detailed petrographic investigations have shown the limestones are variably cemented by rare uneven acicular spar fringes, poorly to well-developed syntaxial rim cements about echinoderm fragments, and equant/blocky microsparite. Staining of thin sections and cathodoluminescence petrography show these spar cement generations are non-ferroan and their very dull- to non-luminescent nature supports precipitation from Mn-poor oxygenated waters, likely of an either meteoric or combined marine/shallow burial origin. Micrite is the dominant intra- and inter-particle pore fill and occurs both as a microbioclastic matrix and as precipitated homogenous and/or micropeloidal cement. The rare fringing cements often seen in association with homogenous and/or micropeloidal micrite may be indicative of true early marine (seafloor) cement precipitation and localised hardground development. An interesting feature of the geology of the Chatham Islands is the occurrence of carbonate material within sedimentary dykes. The locations of the dykes are in association with volcanic and volcaniclastic deposits. Similarities between dyke characteristics at Red Bluff on Chatham Island with mainland occurrences from East Coast and Canterbury Basins (North and South Islands, respectively) on mainland New Zealand have been recognised. They show complex structures including sidewall striations, internal flow structures as revealed by grain sorting, and extra-clast inclusions of previous fill lithologies which are characteristic of carbonate injection. This is in contrast to other dykes which are known to be of a passive fill origin. Multiple phases of carbonate sediment injection can be recognised by crosscutting relationships enabling the determination of a parasequence of events. Possible injection mechanisms are most likely associated with sediment overloading or hydrothermal pressurisation associated with emplacement of submarine volcanics. The Chatham Islands provide an exciting example of a geologically unique and complex non-tropical carbonate depositional setting. The production of carbonates is controlled by volcanic and volcaniclastic sediment input with the types of carbonate deposits and water depth variations related to thermal uplift/subsidence in association with global eustatic sealevel and temperature changes associated with development of Southern Ocean water fronts from the Late Cretaceous-Cenozoic. Carbonate deposition on the Chatham Islands is considered to relate to a rather variable and small scale oceanic, high energy, cool-water carbonate ramp setting whose geometry was continually evolving/changing as a consequence of periodic volcanic episodes.

[pt] A injeção de fluidos é uma prática comum na indústria de petróleo e um dos objetivos desta operação é aumentar o fator de recuperação dos campos petrolíferos. À medida que o óleo vai sendo produzido há naturalmente perda da quantidade de energia nativa, inerente ao reservatório, que manteria a continuidade da produção. Nesse ponto, fazem-se necessárias intervenções nos poços para dar continuidade à produção, lançando-se mão dos métodos de recuperação, dos quais a injeção de fluidos é um deles. As formulações desses fluidos de injeção são via de regra baseadas na utilização de água do mar (que é rica em magnésio) e em solução supercrítica com gás carbônico oriundo do próprio reservatório. Esses fluidos quando em contato com as rochas carbonáticas do pré-sal, propiciam a uma condição de ambiente químico nunca vivenciada quando este tipo de operação era realizada nos reservatórios nacionais anteriores à exploração no pré-sal. As rochas carbonáticas são reativas e a injeção de fluidos pode provocar alterações tanto na composição mineralógica quanto na composição dos fluidos produzidos. O objetivo deste trabalho é buscar evidências objetivas, identificação e quantificação, da precipitação ao longo do tempo de espécies minerais contendo magnésio formadas a partir de interações de rocha calcária (mais especificamente a calcita (CaCO3)) e fluido de injeção utilizado na recuperação avançada de poços de petróleo. Realizaram-se experimentos em que uma rocha calcária conhecida interagiu com CO2 supercrítico em meio a uma solução salina de água do mar sintética sob condições de temperatura e pressão da ordem de grandeza das encontradas em reservatórios do pré-sal. As amostras de rocha foram expostas ao fluido a 150 graus Celsius e 276 bar sob diferentes tempos de reação. Em seguida foram realizados ensaios de DRX e de composição química elementar (ICP-OES) onde ficou evidenciada a presença de magnésio na calcita após interação com o fluido de injeção, as análises por DRX não conseguiram constatar alterações na estrutura cristalina dessas calcitas pós reação. / [en] Fluid injection is a common practice in oil industry and one of its targets is to increase the recovery factor of oil fields. As the oil is being produced, there is naturally loss in the amount of the reservoir native energy to sustain production. At this point, human intervention is necessary to continue production, so recovery methods are used, of which fluid injection is one of them. These injection fluid formulations are usually based on seawater (which is rich in magnesium) and supercritical carbon dioxide solution from the reservoir itself, which in contact with the pre-salt carbonate rocks will lead to a condition of chemical environment never experienced when this operation was performed in national reservoirs prior to presalt exploration. The carbonate rocks are reactive and fluid injections can cause changes in both mineral composition and produced fluids composition. This work objectives the searching for evidences, identification and quantification, of mineral species precipitation containing magnesium from interactions of limestone (more specifically calcite (CaCO3)) and injection fluid used in the enhanced oil recovery. Experiments were performed in which a known powdered limestone rock interacted with supercritical CO2 in a saline solution of synthetic sea water under tipical conditions (temperature and pressure) found at pre-salt reservoirs. The rock samples were exposed to fluid at 150 Celsius degrees and 276 bar under different reaction times. Then, XRD analysis and elemental chemical composition (ICP-OES) tests were performed, showing the presence of magnesium in the calcite after interaction with the injection fluid, although the XRD analysis failed to verify changes in the crystalline structures of these calcites after reaction.

M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology): Vaal University of Technology / Strict environmental regulation on flue gas emission has led to the implementation of FGD technologies in power stations. Wet FGD technology is commonly used because it has high SO2 removal efficiency, high sorbent utilization and due to availability of the sorbent (limestone) used. SO2 is removed by passing flue gas through the absorber where it reacts with the slurry containing calcium ions which is obtained by dissolution. This study presents the findings of the dissolution of a calcium-based material (limestone) for wet FGD process. This was done using a pH stat apparatus and adipic acid as acid titrant. Adipic acid was used because of its buffering effect in wet FGD process. The conditions used for this study are similar to what is encountered in a wet FGD process. The extent of dissolution was determined by analyzing the amount of calcium ions in solution at different dissolution periods. The dissolution kinetics were correlated to the shrinking core model and it was found out that chemical reaction at the surface of the particle is the rate controlling step. This study also investigated the dissolution of coal fly ash and bottom ash. Their dissolution kinetics showed that the diffusion through the product layer was the rate controlling step due to an ash layer formed around the particle. The formation of ash layer was attributed to pozzolanic reaction products which is calcium-alumino-silicate (anorthite) compounds were formed after dissolution. The effect of fly ash on the dissolution of rate of limestone was also studied using response surface methodology. Limestone reactivity was found to increase with increase in the amount of fly ash added and the pH was found to be strong function of the rate constant compared to other dissolution variables. The presence of silica and alumina in fly ash led to a significant increase in the specific surface area due to hydration products formed after dissolution. / Eskom

Cette étude traite du vieillissement des ouvrages en pierres calcaires en interaction avec leur environnement, en se basant à la fois sur la caractérisation des matériaux et des conditions climatiques locales. L’objectif de cette thèse est d’étudier le rôle des conditions climatiques sur la dégradation des pierres par une estimation quantitative du poids des différents processus physiques de dégradation : gel-dégel, condensation and dilatations hygro-thermiques empêchées. Deux sites majeurs ont été sélectionnés : le Château de Chambord en France et le site d’Al-Namrud en Irak, qui est une ancienne capitale assyrienne datant de 1280 BC. Les matériaux français étudiés sont le tuffeau et la pierre de Richemont, qui a été abondamment utilisée comme pierre de substitution durant les restaurations du 20ème siècle. Les matériaux irakiens utilisés sont issus de prélèvements sur des pierres d’origines altérées, des pierres d’origine saines, ainsi que la pierre candidate pour la restauration du site. L’approche choisie pour l’estimation du risque d’endommagement commence par la réalisation d’une campagne expérimentale de caractérisation multi-physiques et multi-échelles des pierres calcaires utilisées à Chambord, ajouté à la collecte des données météorologiques à Chambord grâce à une station et des mesures dans la pierre. L’estimation du risque d’endommagement est obtenue en combinant l’utilisation des données climatiques et de la caractérisation des matériaux, grâce au calcul de l’impact des différents processus physiques de dégradation, qui a nécessité plusieurs développements méthodologiques. La méthodologie proposée pour l’estimation du risque d’endommagement est ensuite appliquée au site d’Al-Namrud. Finalement, un carnet de santé numérique préliminaire du plus édifiant monument d’Al-Namrud – la Ziggurat – est réalisé pour son diagnostic de durabilité. / This study deals with the ageing of limestone structures as a result of the interaction with their environment. It is based on the characterization of both the material and the local climatic conditions. The objective of this thesis is to study the role of climatic conditions in the degradation of stone by quantitative estimation of the weight of the different physical weathering processes: freezing-thawing, condensation and restrained hygro-thermal dilations. Two major historic sites were selected: the Château of Chambord in France and the site of Al-Nimrud City in Iraq, an ancient Assyrian capital, built in 1280 BCE. The French materials studied are tuffeau and Richemont stone, extensively used as a substitute for tuffeau restoration during part of the 20th century. The Iraqi materials studied are samples cored in situ in original weathered stones, original healthy stones, and the stone that could be used as a substitute for restoration. The approach chosen for damage risk assessment starts by the realization of a multiphysics and multiscale experimental characterization campaign of the limestone used at Chambord, added to the collection of meteorological data at Chambord thanks to a weather station supplemented by situ stone measurements. The damage risk assessment is obtained by the combined use of climate data and material characterization, through the calculation of the impact of thedifferent physical weathering processes, which required some methodological developments. The proposed damage risk assessment methodology is then applied to Al-Nimrud site. Finally, a preliminary digital health record of the most prominent monument of Al-Nimrud - the Al-Ziggurat - is carried out to diagnose its durability.

<p> </p><p>The today quarry planning at Klinthagen is rough, which provides an opportunity to introduce new exciting methods to improve the quarry gain and efficiency. Nordkalk AB, active at Klinthagen, wishes to start a new quarry at a nearby location. To exploit future quarries in an efficient manner and ensure production quality, multivariate statistics may help gather important information.</p><p>In this thesis the possibilities of the multivariate statistical approaches of Principal Component Analysis (PCA) and Partial Least Squares (PLS) regression were evaluated on the Klinthagen bore data. PCA data were spatially interpolated by Kriging, which also was evaluated and compared to IDW interpolation.</p><p>Principal component analysis supplied an overview of the variables relations, but also visualised the problems involved when linking geophysical data to geochemical data and the inaccuracy introduced by lacking data quality.</p><p>The PLS regression further emphasised the geochemical-geophysical problems, but also showed good precision when applied to strictly geochemical data.</p><p>Spatial interpolation by Kriging did not result in significantly better approximations than the less complex control interpolation by IDW.</p><p>In order to improve the information content of the data when modelled by PCA, a more discrete sampling method would be advisable. The data quality may cause trouble, though with sample technique of today it was considered to be of less consequence.</p><p>Faced with a single geophysical component to be predicted from chemical variables further geophysical data need to complement existing data to achieve satisfying PLS models.</p><p>The stratified rock composure caused trouble when spatially interpolated. Further investigations should be performed to develop more suitable interpolation techniques.</p>

Hydrogeologic investigations were conducted on the drainage systems of an area of the Pennyroyal sinkhole plain of south central Kentucky. The degree of karstification of five area streams was studied to develop an understanding of the evolution of drainage as the landscape changes from a sandstone caprock plateau to a limestone sinkhole plain. The Chester Upland, capped by the Big Clifty Sandstone, possesses predominantly surface drainage and the Pennyroyal Plain, formed on Mississippian limestones, possesses considerable subsurface drainage. As the Chester Upland Escarpment retreats and surface streams are onto the limestones, the streams evolve to become subsurface streams. The five streams observed in the study (all flowing on limestones) demonstrated less karst development close to the Chester Escarpment and more karst development with increasing distance from the escarpment. Sediments derived from the escarpment and plateau blanket the stream beds thus perching the streams and preventing chemically aggressive water from forming karst solution features in the limestones. The streams farther away from the escarpment are removed from the sediment source and are therefore able to downcut into the limestone and invade the subsurface to become cave streams. Lithologic investigation of limestones exposed in stream beds revealed that minor resistant units can act to diminish downcutting and maintain short sections of surface flow. The stream investigated was not flowing on a perching layer, but instead was held on the surface by a stratigraphic control (spillover layer) that prevented subterranean stream invasion. Dye traces conducted on groundwater flow in the sinkhole plain revealed that the area drainage pattern is changing as surface streams invade the subsurface and that integration between drainage basins is taking place. Stream piracy and stream diversion are occurring in the subsurface causing alteration of the existing topographic drainage divides that developed before the surface streams invaded the subsurface. A general model is presented which shows the evolution of surface drainage to subsurface drainage, as the Chester Escarpment continues its northwestward retreat.