Dissertations / Theses on the topic 'Mineral precipitation'

Fractures are often leakage pathways for fluids through low-permeability rocks that otherwise act as geologic barriers to flow. Flow of fluids that are in chemical disequilibrium with the host rock can lead to mineral precipitation, which reduces fracture permeability. When fracture surfaces contain a single mineral phase, mineral precipitation leads to fast permeability reduction and fracture sealing. However, the feedback between precipitation and permeability may be disrupted by mineral heterogeneities that localize precipitation reactions and provide paths of low-reactivity for fluids to persist over relatively long time-scales. In this dissertation, I explore the role of mineral heterogeneity on precipitation-induced permeability reduction in fractures. To do this, I use a combined experimental and numerical approach to test three hypotheses: (1) Mineral heterogeneity prolongs fracture sealing by focusing flow into paths with limited reactive surface area, (2) Precipitation-induced transport alterations at the fracture-scale are controlled by three-dimensional growth dynamics at the grain-scale, and (3) The effects of mineral heterogeneity become more pronounced as mineralogy and surface roughness become autocorrelated over similar length-scales.

Direct measurements of mineral precipitation using transmitted light methods in a transparent analog fracture show that mineral heterogeneity can lead to the progressive focusing of flow into paths with limited reactive surface area, which is in support of (1). In this experiment, flow focusing led to a 72% reduction in the max precipitation rate; measurements of the projected mineralogy show that this was due to focusing of large dissolved ion concentrations into regions that contained 82% less reactive surface area than the fracture-scale average. Results from a newly developed reactive transport model that simulates precipitation-induced fracture surface alterations as a three-dimensional process are in good qualitative agreement with these experimental observations. Comparison of these results with a reactive transport model that represents precipitation as a 1D alteration of the fracture surfaces show that this flow-focusing process is driven by lateral growth of reactive minerals across the fracture-plane, which supports (2). Lastly, results from simulations in fractures that contain varied degrees of heterogeneity show that precipitation leads to a competition between two feedbacks: (i) precipitation-induced reactive surface area enhancement, which increases precipitation rates, and (ii) precipitation-induced permeability reduction, which decreases precipitation rates. When surface roughness and mineral heterogeneity provide persistent paths of limited surface area, the reactive transport becomes very sensitive to local permeability reduction. Simulation results show that this prolongs the fracture-sealing process and can lead to a reduction in fracture-scale precipitation rate, which supports (3). Furthermore, the results presented in this dissertation demonstrate that predictions of fracture sealing by mineral precipitation can be easily misinformed by studies that ignore small-scale mineral heterogeneity and neglect the three-dimensional nature of precipitation-induced fracture surface alterations.

The injection of CO2 in oil reservoirs for tertiary oil recovery is one of the main Enhanced Oil Recovery (EOR) processes and it is widely used in the oil and gas industry. To prevent early gas breakthrough, CO2 is commonly injected in alternated slugs with water, in a process known as CO2 Water Alternating Gas (CO2 WAG). When such processes are carried out in carbonate reservoirs, there is the potential for calcite (CaCO3) dissolution in the reservoir and its subsequent re-precipitation in production systems, thus posing a flow assurance risk that must be carefully managed. A new thermodynamic model that addresses all of the major steps involved in the precipitation of CaCO3 scale in CO2 WAG production systems is proposed, including: i) the dissolution of injected CO2 into the reservoir brine; ii) the rock-brine interactions and the dissolution of CaCO3 rock; iii) the reactive flow and transport of aqueous components in the reservoir; iv) the partition of components between the liquid, vapour, and water phases; and v) the precipitation of CaCO3 scale as a function of decreasing pressure (and temperature) in CO2 WAG production systems (i.e. in the well and in topside equipment). Thus, an aqueous electrolyte model has been implemented and coupled with a Vapour-Liquid Equilibrium (VLE) model, a multiphase flash model, and a reactive transport model. The non-ideal behaviour of the aqueous and hydrocarbon phases (vapour and liquid) has been modelled by using respectively the Pitzer equations and an Equation of State (EOS) (Soave-Redlich-Kwong, SRK, and Peng-Robinson, PR, EOS, have been used, among others). The implementation of these models has been validated by comparing results with experimental data and/or with results obtained by using industry standard software. In addition, the impact of VLE, multiphase flash, and reactive transport calculations on the precipitation of CaCO3 scale has been investigated, by considering commonly available production data. Also, a procedure had been devised to address each step involved in the precipitation of CaCO3 scale in CO2 WAG production wells individually, and together in an integrated approach. In fact, this work focuses on building the boundaries for the CaCO3 scaling system, thus allowing to define, and work on, worst case scenarios. This gives the required information – both qualitatively and quantitatively – to manage CaCO3 scale in CO2 WAG production wells.

Etude par rmn en phase solide et par analyses d'images de microscopie electronique. Evaluation du pourcentage des differentes especes, de la densite en hydroxyles et de leur evolution en fonction d'un traitement thermique determine. Etude de la structure geometrique des surfaces apres griffage de petites molecules (diols et alcools). Proposition d'un modele ou la surface des silices de precipitation est constitue d'une couche tres desorganisee d'epaisseur donnee. Caracterisation des projections bidimensionnelles des agregats de silice par des exposants fractals, a partir des micrographies electroniques

L’un des enjeux principaux dans l’appréhension de l’évolution du climat planétaire réside dans la compréhension du rôle des processus de formation de la glace ainsi que leur rôle dans la formation et l’évolution des nuages troposphériques. Un cold stage nouvellement construit permet l’observation simultanée de jusqu’à 200 gouttes monodispersées de suspensions contenant des particules de K–feldspath, connues comme étant des particules glaçogènes très actives. Les propriétés glaçogènes des particules résiduelles de chaque goutte sont ensuite comparées pour les différents modes de glaciation et le lien entre noyau glaçogène en immersion et en déposition est étudié. Les premiers résultats ont montré que les mêmes sites actifs étaient impliqué dans la glaciation par immersion et par déposition. Les implications atmosphériques des résultats expérimentaux sont discutés à l’aide de Descam (Flossmann et al., 1985), un modèle 1.5–d à microphysique détaillée dans une étude de cas visant à rendre compte du rôle des différents mécanismes de glaciation dans l’évolution dynamique du nuage convective CCOPE (Dye et al., 1986). Quatre types d’aérosol minéraux (K–feldspath, kaolinite, illite et quartz) sont utilisés pour la glaciation en immersion, par contact et par déposition, à l’aide de paramétrisations sur la densité de sites glaçogènes actifs. Des études de sensibilité, où les différents types d’aérosols et modes de glaciation sont considérés séparément et en compétition, permettent de rendre compte de leurs importances relatives. La glaciation en immersion sur les particules de K–feldspath s’est révélée comme ayant le plus d’impact sur l’évolution dynamique et sur les précipications pour un nuage convectif
One of the main challenges in understanding the evolution of Earth's climate resides in the understanding the ice formation processes and their role in the formation of tropospheric clouds as well as their evolution. A newly built humidity-controlled cold stage allows the simultaneous observation of up to 200 monodispersed droplets of suspensions containing K-feldspar particles, known to be very active ice nucleating particles. The ice nucleation efficiencies of the individual residual particles were compared for the different freezing modes and the relationship between immersion ice nuclei and deposition ice nuclei were investigated. The results showed that the same ice active sites are responsible for nucleation of ice in immersion and deposition modes.The atmospheric implications of the experimental results are discussed, using Descam (Flossmann et al., 1985), a 1.5-d bin-resolved microphysics model in a case study aiming to assess the role of the different ice nucleation pathways in the dynamical evolution of the CCOPE convective cloud (Dye et al., 1986). Four mineral aerosol types (K-feldspar, kaolinite, illite and quartz) were considered for immersion and contact freezing and deposition nucleation, with explicit Ice Nucleation Active Site density parameterizations.In sensitivity studies, the different aerosol types and nucleation modes were treated seperately and in competition to assess their relative importance. Immersion freezing on K-feldspar was found to have the most pronounced impact on the dynamical evolution and precipitation for a convective cloud

Geologic sequestration of carbon dioxide (CO 2) in a deep, saline aquifer is being proposed for a power-generating facility in Florida as a method to mitigate contribution to global climate change from greenhouse gas (GHG) emissions. The proposed repository is a brine-saturated, dolomitic-limestone aquifer with anhydrite inclusions contained within the Cedar Keys/Lawson formations of Central Florida. Thermodynamic modeling is used to investigate the geochemical equilibrium reactions for the minerals calcite, dolomite, and gypsum with 28 aqueous species for the purpose of determining the sensitivity of mineral precipitation and dissolution to the temperature and pressure of the aquifer and the salinity and initial pH of the brine. The use of different theories for estimating CO2 fugacity, solubility in brine, and chemical activity is demonstrated to have insignificant effects on the predicted results. Nine different combinations of thermodynamic models predict that the geochemical response to CO2 injection is calcite and dolomite dissolution and gypsum precipitation, with good agreement among the quantities estimated. In all cases, CO2 storage through solubility trapping is demonstrated to be a likely process, while storage through mineral trapping is predicted to not occur. Over the range of values examined, it is found that net mineral dissolution and precipitation is relatively sensitive to temperature and salinity, insensitive to CO2 injection pressure and initial pH, and significant changes to porosity will not occur.

Swine production represents approximately 40% of the world's meat production, and its wastes contain high concentrations of organic carbon, nitrogen (N), and phosphorus (P). Anaerobic digestion is an increasingly popular technology for treating animal wastes while simultaneously generating energy. Its propagation and ability to solubilize organic N and P make adding a struvite recovery process attractive. Recovering struvite (MgNH4PO4) from anaerobically digested swine waste can address global P shortages, meet P discharge guidelines, and produce slow-release fertilizer, which can be sold for revenue. Anaerobic digesters were operated with at organic loading rates of 3.4-3.9 g volatile solids per liter per day to provide consistent effluent for struvite precipitation studies. Three research questions about struvite precipitation were addressed in this study, specifically what is the (1) required Mg:PO4 ratio, (2) effect of organic matter, and (3) effect of storage time and conditions on struvite precipitation from effluent of anaerobically digested swine manure? Mg:PO4 ratios between 1.3-1.8 were determined to be the economic optimum and precipitated 81-90% of P from synthetic wastewater with calcium phosphate minerals dominating. Under P-limited conditions, a chemical equilibrium model (Visual MINTEQ v.3.0) predicted over 99% P removal with a precipitate mixture of struvite, calcium phosphates, and magnesite. Synthetic wastewater experiments without organic matter removed approximately 85% P with a precipitate mixture of struvite, dolomite, calcite, brucite, and calcium phosphates. Real swine effluent removed more than 95% of P and had a similar mixture of precipitates as synthetic wastewater, but in different concentrations. Organic acids were suspected to prevent struvite formation. Stored anaerobically digested swine wastewater under varying conditions all suggest calcium phosphates form naturally over time. Precipitation of struvite is best carried out as soon as possible to increase the purity of struvite. Although struvite recovery was possible, the conditions for struvite precipitation must be controlled carefully to obtain highly pure struvite.

My research has focused on the precipitation of iron minerals, mostly oxides and hydroxides, in aqueous systems across steep pH and Eh gradients. Unlike most work in this area, which involves loose precipitates filtered out of solutions, I have focused on precipitated aggregates and, more specifically, on those that are self-organized into dis-crete structures or patterns. This topic is actually quite narrow because such types of natu-ral material organization are rare within the geochemical realm compared with the mor-phological richness of crystals, not to mention the phantasmagoria of life.My investigation of iron-based examples has included three types of physical sys-tems: 1) growth of tubular structures around bubbles coming off a charged cathode in a free solution where convection dominates; 2) development of Liesegang patterns within gelled solutions due to reactions dominated by diffusion; and 3) formation of a cement-ing matrix within the aqueous interface between particles of silica. The third case in-volves physical characteristics of the first two in that it is primarily a tightly packed, dif-fusion-limited process, but at least initially the generation of gases can create mechani-cally driven flows through the interstitial spaces.All three systems and studies are inextricably related for both tubular ('vermi-form') structures and Liesegang patterns are commonly found in natural iron-cemented sediments such as massive laterite, ironstone deposits, and banded iron formations. They are also found on a much smaller scale within discrete 'concretions' and represent the two poles of the gradient between convection-based and diffusion-based systems. As Seilacher (2001) states concerning concretions, "the distribution and precipitation of dis-solved constituents, such iron and manganese, proceeds in two radically different mor-phospaces, which are typified by dendrites [and I would include tubes and other linear growth] on the one hand and Liesegang rings on the other." Both have been observed in my lab creations with surprising frequency and tenacity even in systems thought to be in-hibitory.

Les signatures isotopiques des minéraux carbonatés sont utilisées pour caractériser de nombreux processus géochimiques. Cette thèse a pour but de déterminer les vitesses auxquelles ces signatures isotopiques peuvent être altérées lors des interactions entre les fluides et les minéraux. A cette fin, une série d'études expérimentales a été conduite avec la dolomite (CaMg(CO3)2), la magnésite (MgCO3) et la calcite (CaCO3). On a mesuré l'évolution temporelle des compositions isotopiques de Ca et Mg pendant une série d'expériences de dissolution en réacteur fermé de la dolomite à des températures de 50°C à 126°C. A T < 120°C la composition isotopique du calcium dans la phase fluide est identique à celle de la dolomite initiale, mais au-delà de cette température, la signature isotopique du calcium dans le fluide (delta(44/42)Ca fluid) après 4 semaines était 0.6±0.1‰ plus lourde que l'originale. En revanche, le rapport delta(26/24)Mg du fluide reste égal à celui de la dolomite à toutes les températures étudiées. Ces résultats indiquent un double transfert de calcium vers et depuis la structure de la dolomite à T > 120°C. En outre, ces résultats suggèrent que la difficulté de la dolomite à précipiter à température ambiante doit être la conséquence de l'incapacité de Mg à s'incorporer dans la structure du minéral. Dans une autre étude on a conduit des expériences de dissolution de la magnésite à 25°C en solution aqueuses pour différents pH et pression de CO2. On a trouvé que la composition isotopique du fluide à proximité de l'équilibre chimique était différente de celle du solide, ce qui reflète un double transfert de Mg en direction et hors du minéral à température ambiante. Cependant, un seul mécanisme de fractionnement ne peut expliquer le comportement isotopique de Mg observé. La dernière partie de ce travail, consacrée au fractionnement isotopique du carbone dans le système calcite-eau, montre une évolution du fractionnement isotopique de cet élément vers le fractionnement isotopique à l'équilibre d'une durée d'une année après l'atteinte de l'équilibre chimique entre la calcite et l'eau. Les vitesses de rééquilibrage des isotopes de carbone sont ainsi quatre ordres de grandeurs plus lentes que la vitesse d'équilibrage de la calcite avec la solution. Ceci suggère que l'étape limitante dans le processus de rééquilibrage des isotopes du carbone est le transport de cet élément dans le cristal après l'échange isotopique à la surface de ce dernier. Les résultats de cette thèse indiquent que la signature isotopique de Mg, Ca et C des carbonates n'est pas invariante à l'échelle des temps géologiques et qu'elle peut être altérée durant l'interaction de ces minéraux avec l'eau. Ainsi, la préservation des signatures isotopiques des carbonates requiert d'une faible perméabilité des roches ou bien quelque mécanisme inhibant les échanges des métaux et du carbone à la surface des cristaux
The isotopic signatures of carbonate minerals have been applied to illuminate a plethora of natural geochemical processes. This thesis is aimed to assess the rates and or conditions at which such isotope signatures might be altered by fluid-mineral interaction through a series of systematic experimental studies performed with dolomite (CaMg(CO3)2) magnesite (MgCO3) and calcite (Ca-CO3). Ca and Mg isotopic compositions were measured as a function of time during closed-system stoichiometric dolomite dissolution experiments at 50 to 126°C. Although identical to that of the original dolomite at low temperatures, at temperatures >120 °C, the calcium isotopic signature of fluid phase (delta(44/42)Ca fluid) became 0.6±0.1‰ higher than that of the dissolving dolomite over a 4-week period. In contrast, the delta(26/24)Mg fluid, remained equal to that of the dolo-mite both at low and high temperatures. This set of experiments evidences the two-way transfer of calcium in and out of the dolomite structure at elevated temperatures. The results suggest that the inhability of dolomite to precipitate at these conditions is due to the difficulty of Mg to be reincorporated in the dolomite structure. In a follow-up study, magnesite was dissolved at 25°C in the presence of fluids with distinct pH and CO2 pressures. The isotopic compositions of the fluid differed from that of the solid at near-to chemical equilibrium indicating the two-way transfer of magnesium into this mineral at ambient temperatures. A single fractionation mechanism cannot explain the distinct Mg isotope behaviors observed. Further work on carbon isotope exchanges in the calcite water system shows a slow by steady evolution of the carbon isotopic composition towards the accepted equilibrium fractionation factor over the course of nearly year-long experiments after the system had attained bulk chemical equilibrium. Carbon isotope reequilibration rates were found to be approximately four orders of magnitude slower than that of bulk calcite dissolution, suggesting that the rate limiting step to the carbon isotope reequilibration process is the transport of carbon into and out of the bulk mineral after it has exchanged on the surface. The results of this thesis suggest that the Mg, Ca and C isotopic signatures in carbonate minerals are not invariant over geological time-frames and can be readily altered by water-mineral interaction. Such results indicate that the preservation of carbonate mineral signatures require low permeability rock formations or some inhibitory mechanism limiting metal and carbon exchange

Ce travail met en evidence, a partir de mesures de terrain, les principaux facteurs de variation des concentrations des especes minerales dans les precipitations que l'on peut attribuer a deux causes principales: la variation des emissions des sources et celle des facteurs de couplage entre aerosol et precipitation

L'altération chimique des roches primaires et des minéraux dans les systèmes naturels a un impact majeur sur la formation des sols et leur composition. L'altération chimique est largement pilotée par la dissolution des minéraux. Les éléments chimiques libérés dans les eaux souterraines par la dissolution des minéraux réagissent facilement pour former des minéraux secondaires comme les argiles, zéolites et carbonates. Les carbonates se forment par réaction des cations divalents (Ca, Fe et Mg) avec CO2 dissous tandis que la formation des kaolins et de la gibbsite est attribuée à l'altération des minéraux riches en aluminium, le plus souvent les feldspaths. Le projet Carbfix à Hellisheiði (sud-ouest de l'Islande) a pour but d'utiliser les processus d'altération naturelle pour former des minéraux carbonatés par réinjection dans les roches basaltiques environnantes de CO2 provenant d'une centrale géothermique. Ce processus trouve son origine dans la dissolution des roches basaltiques riches en cations divalents (Ca, Fe et Mg) qui se combinent au CO2 injecté pour former des minéraux carbonatés. Cette thèse est centrée sur la dissolution du basalte cristallin de Stapafell qui est composé essentiellement de trois phases minérales (plagioclase, pyroxène et olivine) et qui est riche en cations divalents. La vitesse de libération des éléments du basalte à l'état stationnaire et loin de l'équilibre a été mesurée dans des réacteurs à circulation à des pH de 2 à 12 et des températures de 5 à 75°C. Les vitesses de libération de Si et Ca à l'état stationnaire présentent une variation en fonction du pH en forme de U avec une diminution des vitesses lorsque le pH augmente en conditions acides et une augmentation avec le pH en conditions alcalines. Les vitesses de libération du silicium par le basalte cristallin sont comparables à celles par le verre basaltique de même composition chimique aux faibles pH et aux températures = 25°C mais elles sont plus lentes aux pH alcalins et aux températures = 50°C. Par contre, les vitesses de libération de Mg et Fe diminuent de manière monotone avec l'accroissement du pH à toutes les températures. Ce comportement a pour cause les variations contrastées, en fonction du pH, des vitesses de dissolution des trois minéraux constitutifs du basalte: plagioclase, olivine et pyroxène. Les vitesses de libération des éléments déduites de la somme des vitesses de dissolution du plagioclase, pyroxène et olivine normalisées à la fraction volumique de ces minéraux sont, à un ordre de grandeur près, les mêmes que celles mesurées dans cette étude. En outre, les résultats expérimentaux montrent que, durant l'injection d'eaux chargées en CO2 de pH proche de 3. 6, le basalte cristallin libère préférentiellement Mg et Fe en solution par rapport à Ca. L'injection de fluides acides chargés en CO2 dans des roches cristallines basaltiques peut donc favoriser la formation de carbonates de Mg et Fe aux dépends de la calcite aux conditions de pH acides à neutres. Le plagioclase, qui est la phase la plus abondante du basalte, influence fortement la réactivité de ce dernier. La vitesse de dissolution du plagioclase, basée sur la libération de la silice, présente une variation en forme de U en fonction du pH, diminuant lorsque le pH augmente aux conditions acides mais augmentant avec le pH aux conditions alcalines. En accord avec les données de la littérature, la vitesse de dissolution du plagioclase à pH constant, en conditions acides, augmente avec sa teneur en anorthite. L'interprétation et le fit des données obtenues suggèrent que la vitesse de dissolution du plagioclase est contrôlée par la décomposition d'un complexe activé riche en silice, formé par le départ de Al de la structure du minéral. Le plus remarquable, par comparaison aux hypothèses antérieures, est que la vitesse de dissolution du plagioclase en conditions alcalines est indépendante de sa teneur en anorthite - e. G. Les vitesses de dissolution des plagioclases riches en anorthite augmentent avec le pH aux conditions alcalines. A ces conditions, il est probable que la vitesse de dissolution rapide du plagioclase domine, en raison de sa forte teneur en Ca, la libération vers la phase fluide des cations divalents du basalte cristallin. La gibbsite est généralement le premier minéral qui précipite lors de la dissolution du plagioclase. C'est un hydroxyde d'aluminium que l'on trouve dans divers sols et qui est aussi la phase principale des minerais de bauxite. Les vitesses de précipitation de la gibbsite ont été mesurées dans des réacteurs fermés, en conditions alcalines à 25 et 80°C, en fonction de l'état de saturation du fluide. Les analyses des solides après réaction ont démontré que la précipitation de gibbsite s'est produite dans toutes les expériences. L'interprétation de l'évolution dans le temps de la chimie du fluide réactif fournit des vitesses de précipitation de la gibbsite qui sont près des vitesses de dissolution du plagioclase. En plus, des vitesses de précipitation de la gibbsite diminuent plus rapidement que des vitesses de dissolution du plagioclase quand le pH descende. Ceci suggère que l'étape limitant de l'altération du plagioclase sur la surface de la terre est plutôt la consommation d'Al par formation de la gibbsite que la dissolution même du plagioclase. La kaolinite est en général le second minéral formé après la gibbsite lors de la dissolution du plagioclase à basse température. Les vitesses de précipitation de la kaolinite ont été mesurées dans des réacteurs à circulation à pH = 4 et t = 25°C, en fonction de l'état de saturation du fluide. Au total, 8 expériences de précipitation de longues durées ont été réalisées dans des fluides légèrement supersaturés par rapport à la kaolinite, en utilisant comme germes pour la précipitation une quantité connue de de kaolinite de Géorgie (KGa-1b) contenant peu de défauts et préalablement nettoyée. Les vitesses de précipitation de kaolinite mesurées sont relativement lentes comparées aux vitesses de dissolution du plagioclase. Cette observation suggère que la formation de kaolinite lors de l'altération est limitée par sa vitesse de précipitation plutôt que par que la disponibilité en Al et Si issus de la dissolution du plagioclase. L'ensemble des résultats de cette étude fournit un certain nombre de principes scientifiques de base nécessaires à la prédiction des vitesses et des conséquences de la dissolution du basalte cristallin et du plagioclase à la surface de la Terre et lors de l'injection du CO2 à proximité de la surface dans le cadre des efforts de stockage du carbone. Les résultats obtenus indiquent, bien que les vitesses de précipitation de la gibbsite soient relativement rapides, que la vitesse de précipitation relativement lente de la kaolinite peut être le processus contrôlant la formation de ce minéral à la surface de la Terre. Cette observation souligne la nécessité de poursuivre la quantification de la précipitation de ce minéral secondaire aux conditions typiques de la surface de la Terre. En outre, comme les proportions des différents métaux divalents libérés par les basaltes cristallins varient sensiblement avec le pH, la carbonatation des basaltes doit produire un changement systématique de l'identité des minéraux carbonatés et des zéolites précipités en fonction de la distance au puits d'injection. Cette dernière conclusion pourra être directement testée dans le cadre du projet CarbFix actuellement conduit à Hellisheiði en Islande
The chemical weathering of primary rocks and minerals in natural systems has a major impact on soil development and its composition. Chemical weathering is driven to a large extent by mineral dissolution. Through mineral dissolution, elements are released into groundwater and can readily react to precipitate secondary minerals such as clays, zeolites, and carbonates. Carbonates form from divalent cations (e. G. Ca, Fe and Mg) and CO2, and kaolin clay and gibbsite formation is attributed to the weathering of aluminium- rich minerals, most notably the feldspars. The CarbFix Project in Hellisheiði SW-Iceland aims to use natural weathering processes to form carbonate minerals by the re-injection of CO2 from a geothermal power plant back into surrounding basaltic rocks. This process is driven by the dissolution of basaltic rocks, rich in divalent cations, which can combine with injected CO2 to form and precipitate carbonates. This thesis focuses on the dissolution behaviour of Stapafell crystalline basalt, which consists of three major phases (plagioclase, pyroxene, and olivine) and is rich in divalent cations. Steady-state element release rates from crystalline basalt at far-from-equilibrium conditions were measured at pH from 2 to 11 and temperatures from 5° to 75° C in mixed-flow reactors. Steady-state Si and Ca release rates exhibit a U-shaped variation with pH, where rates decrease with increasing pH at acid condition but increase with increasing pH at alkaline conditions. Silicon release rates from crystalline basalt are comparable to Si release rates from basaltic glass of the same chemical composition at low pH and temperatures =25°C but slower at alkaline pH and temperatures =50°C. In contrast, Mg and Fe release rates decrease continuously with increasing pH at all temperatures. This behaviour is interpreted to stem from the contrasting dissolution behaviours of the three major minerals comprising the basalt: plagioclase, pyroxene, and olivine. Element release rates estimated from the sum of the volume fraction normalized dissolution rates of plagioclase, pyroxene, and olivine are within one order of magnitude of those measured in this study. In addition, these experimental results show that during injection of CO2-charged waters with pH close to 3. 6, crystalline basalt preferentially releases Mg and Fe relative to Ca to the fluid phase. The injection of acidic CO2-charged fluids into crystalline basaltic rocks may therefore favour the formation of Mg and Fe carbonates rather than calcite at acidic to neutral conditions. Plagioclase is the most abundant phase in crystalline basalts and thus influences strongly its reactivity. Plagioclase dissolution rates based on Si release show a common U-shaped behaviour as a function of pH where rates decrease with increasing pH at acid condition but increase with increasing pH at alkaline conditions. Constant pH plagioclase dissolution rates increase with increasing anorthite content at acid conditions, in agreement with literature findings. Interpretation and data fitting suggests that plagioclase dissolution rates are consistent with their control by the detachment of Si-rich activated complexes formed by the removal of Al from the mineral framework. Most notably, compared with previous assumptions, plagioclase dissolution rates are independent of plagioclase composition at alkaline conditions, e. G. Anorthite-rich plagioclase dissolution rates increase with increasing pH at alkaline conditions. At such conditions rapid plagioclase dissolution rates likely dominate divalent metal release from crystalline basalts to the fluids phase due to its high Ca content. Gibbsite is commonly the first mineral formed during low temperature dissolution of plagioclase. Gibbsite is an aluminium-hydroxide that is found in various soils as well as the dominant phase in many bauxite ores. Gibbsite precipitation rates were measured in closed system reactors at alkaline condition, both at 25 °C and 80 °C as a function of fluid saturation state. Analyses of the solids demonstrate that gibbsite precipitation occurred in all experiments. The comparison of gibbsite precipitation to the dissolution rates of plagioclase at pH 11 shows that the rates are close to equal. The precipitation rates of gibbsite, however, decrease faster with decreasing pH than plagioclase dissolution rates. As such it seem likely that plagioclase dissolution is faster than gibbsite precipitation at near to neutral pH, and the relatively slow rate of gibbsite precipitation influences plagioclase weathering in many Earth surface systems. Kaolinite is commonly the second secondary mineral formed during low temperature dissolution of plagioclase. Kaolinite precipitation rates were measured in mixed flow reactors as a function of fluid saturation state at pH=4 and 25 °C. In total eight long-term precipitation experiments were performed in fluids mildly supersaturated with respect to kaolinite, together with a known quantity of cleaned low defect Georgia Kaolinite as seeds. Measured kaolinite precipitation rates are relatively slow compared with plagioclase dissolution rates. This observation suggests that kaolinite formation during weathering is limited by its precipitation rates rather than by the availability of aqueous species sourced from plagioclase dissolution. Taken together the results of this study provide some of the fundamental scientific basic for predicting the rates and consequences of crystalline basalt and plagioclase dissolution at both the Earth's surface and during the near surface injection of CO2 as part of carbon storage efforts. Results indicate that although gibbsite precipitation rates are relatively rapid, the relatively slow precipitation rates of kaolinite may be the process controlling the formation of this mineral at the Earth's surface. This observation highlights the need to further quantify this secondary mineral precipitation rates at conditions typical at the Earth's surface. Moreover, as the composition of divalent metals released from crystalline basalts varies significantly with pH, CO2 carbonation in basalt should yield a systematic variation in the identity of carbonate and zeolite minerals precipitated with distance from the injection site. This latter conclusion can be tested directly as part of the currently on-going CarbFix project in Hellisheiði, Iceland

O presente trabalho reúne elementos para projeto de precipitadores eletrostáticos, com dados levantados de cinzas volantes provenientes da combustão de gases em caldeiras de carvão mineral. Os objetivos desta pesquisa são construir um dispositivo padronizado para medição da resistividade ôhmica de materiais, levantar dados de resistividade ôhmica das cinza volantes de carvão mineral utilizado no Brasil e, com estes dados, listar recomendações sobre cuidados no dimensionamento de precipitadores (cálculo da área de captação), quando este equipamento é posicionado após uma caldeira que queima o carvão mineral nacional. A metodologia utilizada foi baseada em norma americana ASME, em que o pó (material a ser testado) é colocado sobre eletrodos de descarga e de coleta, uma alta tensão elétrica é aplicada até atingir a tensão de ruptura elétrica e neste instante é medida a resistividade. A construção do experimento e procedimento de execução foram seguidos conforme esta norma. O material de teste foi coletado de precipitadores eletrostáticos existentes na região Sul do Brasil, onde o carvão mineral tem seu uso freqüente. Os resultados apresentaram baixos valores para resistividade da cinza volante nacional, se comparados com resultados de carvões de outros países. Sua variação em função da temperatura segue a tendência de cinza volantes de outros países, ou seja, aumento da resistividade ôhmica com o aumento da temperatura. Foram realizados também experimentos com material retirado de precipitadores eletrostáticos acoplados a caldeiras de biomassa, que forneceram valores de resistividade ainda menores do que os do carvão mineral nacional. O material de teste, composição química e processo de coleta foram totalmente caracterizados, disponibilizados e uma análise completa pôde ser realizada, fato inédito no Brasil. Esses resultados permitiram listar recomendações visando o projeto de precipitadores eletrostáticos acoplados a caldeiras que queimam carvão mineral nacional.
This report is a collection of elements to be used in the design of Electrostatic Precipitators, with experimental data of fly ashes from combustion gases of Mineral Coal Fired Boilers. The aims of this research are to construct a standard device to measure the ohmic resistivity of materials, to get data of ohmic resistivity of fly ashes from mineral coals used in Brazil and with this data, to list recommendations about the key points to size electrostatic precipitators (calculation of specific collection area), when this equipment is arranged after one boiler that burns Brazilian mineral coals. The method used was based on the ASME Standard, in which the fly ash (material to be tested) is put between the discharge and the collecting electrodes, a high electrical tension is applied until the electrical break down tension to be reached; at this moment, the resistivity is measured. The construction of this device and the experimental procedure were conducted according to this standard. The tested materials were collected from existing Electrostatic Precipitator of South of Brazil, where the mineral coal is commonly used. The results indicated low values of ohmic resistivity of the Brazilian fly ashes, if compared to results of coals from other countries. Its variation with the temperature has the same behavior of fly ashes from other countries, i.e., the ohmic resistivity increases when the temperature increases. It was also executed tests with particulate materials from electrostatic precipitator of biomass boiler whose ohmic resistivity is lower than the Brazilian mineral coal. The tested material, chemical composition, and collecting process were totally described, available and a full analysis can be executed; these data are inedita in Brazil. These results allow to list the recommendations to design Electrostatic Precipitators for Brazil Mineral Coal Fired Boilers.

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A pesquisa desenvolvida tem foco na análise espaço-temporal das secas, baseada em informações de chuvas. Para a obtenção das séries históricas representativas das secas e estudo espacial do fenômeno, foi empregada a análise regional de precipitações com momentos-L, além do índice de seca Standardized Precipitation Index (SPI). Para a análise de séries temporais de secas foi utilizada a transformada de ondaletas, uma alternativa à transformada de Fourier, a qual permite identificar periodicidades nas séries além de localizar variações dessas periodicidades ao longo do tempo. Procurou-se ainda investigar possíveis influências dos fenômenos El Niño Oscilação Sul (ENOS), por meio do Índice Oceânico Niño (ION) e do Índice de Oscilação Sul (IOS), e do fenômeno da Oscilação Decenal do Pacífico (ODP) sobre os índices de secas obtidos. Foi proposto incorporar a análise regional de frequência no cálculo das séries de SPI, com vistas a contribuir com a superação da crítica de que, para esse cálculo, longos registros históricos de chuvas são necessários, além de considerar apenas a possibilidade de uso da distribuição de probabilidades Gama. Reforça-se a necessidade de, no cálculo do SPI, considerar outras possibilidades além dessa distribuição e a análise local de frequências, uma vez que valores extremos de chuvas eventualmente distorcem significativamente as estimativas do índice. Além disso, a análise regional de frequência permitiu definir regiões estatisticamente homogêneas, as quais apresentaram abrangência geográfica inversamente proporcional aos totais precipitados médios anuais. Para a análise de séries temporais o uso da transformada de ondaletas não detectou aumento da frequência de ocorrência de secas na área de estudo nos últimos anos. Além disso, não possibilitou fazer uma conexão clara entre as secas na região de estudo e os índices climáticos IOS, ION e ODP. Ainda assim, de alguma forma, percebeu-se que esses fenômenos de grande escala influenciam a intensidade das secas em escala local, uma vez que foi persistente a observação das secas mais extremas na região em fase fria de ENOS e ODP, corroborando a tese de que extremos climáticos são mais intensos na América do Sul quando o ENOS e ODP estão em fase.

En hydrometallurgie et pyrometallurgie, les solutions contenant de l'arsenic doivent etre traitees en fin de procede. L'objectif de cette etude est l'elimination de l'arsenic par precipitation. Notre travail consiste a hydrolyser le sel mixte d'arsenic et de fer, contenu dans des solutions de biolixiviation issues de minerais d'or, par une solution de ca(oh)#2 ou de naoh. L'hydrolyse aboutit a la formation de colloides qui precipitent. Plusieurs parametres peuvent intervenir dans ce processus, dont les principaux sont: 1) rapport d'hydrolyse (oh)/fe total; 2) rapport molaire fe/as etc. . . Le mecanisme fondamental de l'elimination de l'arsenic s'est revele etre essentiellement relie a la formation d'hydroxydes de fer colloidal, par un processus de nucleation-agregation. C'est pourquoi, nous avons developpe avec des solutions modeles, une etude systematique des conditions de formation de ces especes. Les agregats obtenus presentent une grande surface specifique et, au ph de leur formation, ils sont charges positivement. Ils ont ainsi la possibilite de provoquer la floculation des ions arseniates par attraction electrostatique. Mais on pense egalement a la formation d'un complexe entre les ions arseniates et la surface du fer, comme il a ete montre par des mesures potentiometriques et en microscopie electronique

This research is focused on space-time analysis of droughts, based on rainfall data. In order to obtain time series of droughts, the Standardized Precipitation Index (SPI), a rainfall based drought index was used. The spatial analysis of the phenomenon was based on the regional analysis with L-moments. For the time series studies, the continuous wavelet transform was used. This technique shows up as an alternative to Fourier analysis, to identify periodicities in time series and to find variations of these frequencies over time. Also was sought to investigate possible influences of El Niño Southern Oscillation (ENSO) and Pacific Decadal Oscillation (PDO) on the time series of drought index obtained. It was proposed to incorporate the regional frequency analysis with L-moments for the calculation of the SPI, in order to overcome the necessity of long historical records of rainfall data in order to obtain a good estimative of the SPIs time series. Also a variety of probability distribution functions were tested, besides Gama. In addition, the regional frequency analysis came to define statistically homogeneous, which in general are spread over large areas whose sizes are inversely proportional to the mean values of rainfall. The continuous wavelet transform did not identify an increased frequency of occurrence of droughts in the study area over time. Also, through use of this technique, it was not possible to identify increased intensity of the phenomenon in the study area in recent years. Moreover, the technique did not allow making a clear connection between the droughts in the study area and macro climatic indices used (ENSO and PDO). Yet somehow, it was realized that these macro-scale phenomena may influence the intensity of drought on a local scale, as it was observed persistent cold phase ENSO and PDO in the most extreme drought events in the study area, corroborating the thesis that, when ENSO and PDO are in phase, weather extremes are more intense in South America.
A pesquisa desenvolvida tem foco na análise espaço-temporal das secas, baseada em informações de chuvas. Para a obtenção das séries históricas representativas das secas e estudo espacial do fenômeno, foi empregada a análise regional de precipitações com momentos-L, além do índice de seca Standardized Precipitation Index (SPI). Para a análise de séries temporais de secas foi utilizada a transformada de ondaletas, uma alternativa à transformada de Fourier, a qual permite identificar periodicidades nas séries além de localizar variações dessas periodicidades ao longo do tempo. Procurou-se ainda investigar possíveis influências dos fenômenos El Niño Oscilação Sul (ENOS), por meio do Índice Oceânico Niño (ION) e do Índice de Oscilação Sul (IOS), e do fenômeno da Oscilação Decenal do Pacífico (ODP) sobre os índices de secas obtidos. Foi proposto incorporar a análise regional de frequência no cálculo das séries de SPI, com vistas a contribuir com a superação da crítica de que, para esse cálculo, longos registros históricos de chuvas são necessários, além de considerar apenas a possibilidade de uso da distribuição de probabilidades Gama. Reforça-se a necessidade de, no cálculo do SPI, considerar outras possibilidades além dessa distribuição e a análise local de frequências, uma vez que valores extremos de chuvas eventualmente distorcem significativamente as estimativas do índice. Além disso, a análise regional de frequência permitiu definir regiões estatisticamente homogêneas, as quais apresentaram abrangência geográfica inversamente proporcional aos totais precipitados médios anuais. Para a análise de séries temporais o uso da transformada de ondaletas não detectou aumento da frequência de ocorrência de secas na área de estudo nos últimos anos. Além disso, não possibilitou fazer uma conexão clara entre as secas na região de estudo e os índices climáticos IOS, ION e ODP. Ainda assim, de alguma forma, percebeu-se que esses fenômenos de grande escala influenciam a intensidade das secas em escala local, uma vez que foi persistente a observação das secas mais extremas na região em fase fria de ENOS e ODP, corroborando a tese de que extremos climáticos são mais intensos na América do Sul quando o ENOS e ODP estão em fase.

L'altération chimique des roches primaires et des minéraux dans les systèmes naturels a un impact majeur sur la formation des sols et leur composition. L'altération chimique est largement pilotée par la dissolution des minéraux. Les éléments chimiques libérés dans les eaux souterraines par la dissolution des minéraux réagissent facilement pour former des minéraux secondaires comme les argiles, zéolites et carbonates. Les carbonates se forment par réaction des cations divalents (Ca, Fe et Mg) avec CO2 dissous tandis que la formation des kaolins et de la gibbsite est attribuée à l'altération des minéraux riches en aluminium, le plus souvent les feldspaths. Le projet Carbfix à Hellisheiði (sud-ouest de l'Islande) a pour but d'utiliser les processus d'altération naturelle pour former des minéraux carbonatés par réinjection dans les roches basaltiques environnantes de CO2 provenant d'une centrale géothermique. Ce processus trouve son origine dans la dissolution des roches basaltiques riches en cations divalents (Ca, Fe et Mg) qui se combinent au CO2 injecté pour former des minéraux carbonatés. Cette thèse est centrée sur la dissolution du basalte cristallin de Stapafell qui est composé essentiellement de trois phases minérales (plagioclase, pyroxène et olivine) et qui est riche en cations divalents. La vitesse de libération des éléments du basalte à l'état stationnaire et loin de l'équilibre a été mesurée dans des réacteurs à circulation à des pH de 2 à 12 et des températures de 5 à 75°C. Les vitesses de libération de Si et Ca à l'état stationnaire présentent une variation en fonction du pH en forme de U avec une diminution des vitesses lorsque le pH augmente en conditions acides et une augmentation avec le pH en conditions alcalines. Les vitesses de libération du silicium par le basalte cristallin sont comparables à celles par le verre basaltique de même composition chimique aux faibles pH et aux températures ≥ 25°C mais elles sont plus lentes aux pH alcalins et aux températures ≥ 50°C. Par contre, les vitesses de libération de Mg et Fe diminuent de manière monotone avec l'accroissement du pH à toutes les températures. Ce comportement a pour cause les variations contrastées, en fonction du pH, des vitesses de dissolution des trois minéraux constitutifs du basalte: plagioclase, olivine et pyroxène. Les vitesses de libération des éléments déduites de la somme des vitesses de dissolution du plagioclase, pyroxène et olivine normalisées à la fraction volumique de ces minéraux sont, à un ordre de grandeur près, les mêmes que celles mesurées dans cette étude. En outre, les résultats expérimentaux montrent que, durant l'injection d'eaux chargées en CO2 de pH proche de 3.6, le basalte cristallin libère préférentiellement Mg et Fe en solution par rapport à Ca. L'injection de fluides acides chargés en CO2 dans des roches cristallines basaltiques peut donc favoriser la formation de carbonates de Mg et Fe aux dépends de la calcite aux conditions de pH acides à neutres. Le plagioclase, qui est la phase la plus abondante du basalte, influence fortement la réactivité de ce dernier. La vitesse de dissolution du plagioclase, basée sur la libération de la silice, présente une variation en forme de U en fonction du pH, diminuant lorsque le pH augmente aux conditions acides mais augmentant avec le pH aux conditions alcalines. En accord avec les données de la littérature, la vitesse de dissolution du plagioclase à pH constant, en conditions acides, augmente avec sa teneur en anorthite. L'interprétation et le fit des données obtenues suggèrent que la vitesse de dissolution du plagioclase est contrôlée par la décomposition d'un complexe activé riche en silice, formé par le départ de Al de la structure du minéral. Le plus remarquable, par comparaison aux hypothèses antérieures, est que la vitesse de dissolution du plagioclase en conditions alcalines est indépendante de sa teneur en anorthite - e.g. les vitesses de dissolution des plagioclases riches en anorthite augmentent avec le pH aux conditions alcalines. A ces conditions, il est probable que la vitesse de dissolution rapide du plagioclase domine, en raison de sa forte teneur en Ca, la libération vers la phase fluide des cations divalents du basalte cristallin. La gibbsite est généralement le premier minéral qui précipite lors de la dissolution du plagioclase. C'est un hydroxyde d'aluminium que l'on trouve dans divers sols et qui est aussi la phase principale des minerais de bauxite. Les vitesses de précipitation de la gibbsite ont été mesurées dans des réacteurs fermés, en conditions alcalines à 25 et 80°C, en fonction de l'état de saturation du fluide. Les analyses des solides après réaction ont démontré que la précipitation de gibbsite s'est produite dans toutes les expériences. L'interprétation de l'évolution dans le temps de la chimie du fluide réactif fournit des vitesses de précipitation de la gibbsite qui sont près des vitesses de dissolution du plagioclase. En plus, des vitesses de précipitation de la gibbsite diminuent plus rapidement que des vitesses de dissolution du plagioclase quand le pH descende. Ceci suggère que l'étape limitant de l'altération du plagioclase sur la surface de la terre est plutôt la consommation d'Al par formation de la gibbsite que la dissolution même du plagioclase. La kaolinite est en général le second minéral formé après la gibbsite lors de la dissolution du plagioclase à basse température. Les vitesses de précipitation de la kaolinite ont été mesurées dans des réacteurs à circulation à pH = 4 et t = 25°C, en fonction de l'état de saturation du fluide. Au total, 8 expériences de précipitation de longues durées ont été réalisées dans des fluides légèrement supersaturés par rapport à la kaolinite, en utilisant comme germes pour la précipitation une quantité connue de de kaolinite de Géorgie (KGa-1b) contenant peu de défauts et préalablement nettoyée. Les vitesses de précipitation de kaolinite mesurées sont relativement lentes comparées aux vitesses de dissolution du plagioclase. Cette observation suggère que la formation de kaolinite lors de l'altération est limitée par sa vitesse de précipitation plutôt que par que la disponibilité en Al et Si issus de la dissolution du plagioclase. L'ensemble des résultats de cette étude fournit un certain nombre de principes scientifiques de base nécessaires à la prédiction des vitesses et des conséquences de la dissolution du basalte cristallin et du plagioclase à la surface de la Terre et lors de l'injection du CO2 à proximité de la surface dans le cadre des efforts de stockage du carbone. Les résultats obtenus indiquent, bien que les vitesses de précipitation de la gibbsite soient relativement rapides, que la vitesse de précipitation relativement lente de la kaolinite peut être le processus contrôlant la formation de ce minéral à la surface de la Terre. Cette observation souligne la nécessité de poursuivre la quantification de la précipitation de ce minéral secondaire aux conditions typiques de la surface de la Terre. En outre, comme les proportions des différents métaux divalents libérés par les basaltes cristallins varient sensiblement avec le pH, la carbonatation des basaltes doit produire un changement systématique de l'identité des minéraux carbonatés et des zéolites précipités en fonction de la distance au puits d'injection. Cette dernière conclusion pourra être directement testée dans le cadre du projet CarbFix actuellement conduit à Hellisheiði en Islande.

Lors de l'extraction de l'uranium par lixiviation acide, AREVA fait face à des phénomènes transitoires de précipitation de phases mal cristallisées entrainant un colmatage des installations. Les analyses de ces précipités ont mis en évidence la formation d'un solide jaune minoritaire et d'un blanc majoritaire composé de sulfate de calcium et d'hydroxysulfate d'aluminium. Afin de comprendre les phénomènes menant à la précipitation et pour prévoir, éviter ou limiter leur apparition, les travaux de thèse ont consisté en l'étude expérimentale des équilibres solides-liquide du système complexe Al–Fe–K–P–S–H2O (± Ca et Mg) en milieu acide à 25°C, avec pour objectif l'identification des solides susceptibles d'apparaître en conditions industrielles. Les résultats permettront ainsi de compléter les bases de données thermodynamiques utilisées pour modéliser le comportement global du milieu lors des opérations. Après la mise au point de techniques analytiques appropriées, le travail s'est porté sur la délimitation des équilibres liquide-solides du système relatif au précipité blanc et particulièrement sur l'analyse des ternaires impliquant les hydroxysulfates d'aluminium. Le colmatage se produisant durant la phase d'acidification, l'évolution de la précipitation de ces hydroxysulfates en fonction du pH a été étudiée, afin de caractériser les solides formés en présence de cations minoritaires (Na+, K+, Mg2+, Ca2+) et de définir leurs constantes de solubilités à partir d'un modèle de calcul des coefficients d'activités des ions en solution. Des tests dynamiques sur colonne à partir de minerai naturel ont également été effectués et comparés aux résultats statiques
During the uranium extraction by acid leaching, AREVA observed the precipitation of not well crystallized solid phases, leading to the clogging of various equipment. The analyses of these precipitates highlighted the formation of a minor yellow precipitate and a major white precipitate containing calcium sulphate and aluminium hydroxisulphate. To understand the phenomena leading to the precipitation and to predict, prevent or at least limit their formation, this thesis work consisted of the solid-liquid equilibria experimental study of the Al–Fe–K–P–S–H2O (± Ca and Mg) system in an acidic environment at 25°C, with the identification of solid phases which may appear in natural ore as the major goal. The results could complete the thermodynamic database used to model global behaviour of the environment during acid mining. Based on the observed precipitates, two quaternary systems were defined, such as the H2O-Al3+, Ca2+ // O2-, SO42- system. After the development of appropriate analytical techniques, the work focused on the delimitation of the liquid-solid equilibria of the system based on the white precipitate and particularly on the analysis of the ternaries involving aluminium hydroxisulphates. As clogging occurs during acidification, the hydroxisulphate precipitation depending on the pH was studied in the presence of minority cations (Na+, K+, Mg2+, Ca2+), in order to characterise the solid phases which were formed, and to define their solubility constants. For the solubility constant determination, a calculation model of the ion activity coefficients in solution was used. A dynamic survey on a column containing natural ore was done and compared to static results

Au cours de ces dernières décennies, des études ont étés menées pour identifier plusieurs traceurs des matériaux du cycle du combustible nucléaire, dans le cadre de la lutte contre la prolifération nucléaire. Ces matériaux sont généralement collectés lors d’inspections dans des installations nucléaires, ou saisis lors de contrôles de trafics illicites. Les informations fournies par ces traceurs sont parcellaires et ne permettent pas de déterminer avec exactitude la provenance et l’historique industriel de ces matériaux.Le but de ce travail de thèse est de démontrer le potentiel de l’utilisation des isotopes du molybdène pour le traçage des matériaux du cycle du combustible nucléaire. Le choix s’est porté sur le molybdène car en raison de la similarité de leurs propriétés chimiques, le molybdène et l’uranium sont étroitement associés dans les minerais d’uranium et tout au long de la chaîne de purification de l’uranium. L’étude s’est focalisée sur une partie de l’amont du cycle du combustible, depuis l’extraction des minerais d’uranium jusqu’à la production des concentrés miniers d’uranium : divers procédés physiques et chimiques sont appliqués, à la fois pour purifier l’uranium et abaisser la concentration en molybdène.Au cours de cette étude, une nouvelle méthode de séparation du molybdène a été développée pour caractériser sa composition isotopique dans des minerais, minéraux et concentrés miniers d’uranium. La variabilité des compositions isotopiques du molybdène dans un gisement d’uranium est principalement due aux mécanismes d’adsorption et/ou de précipitation du molybdène. Les gisements magmatiques et sédimentaires ont des compositions isotopiques différentes, ce qui permet ainsi leurs distinctions. Les concentrés miniers d’uranium produits à partir de ces deux types de gisements ont des compositions isotopiques similaires aux minerais. Ces résultats soulignent ainsi le potentiel des isotopes du molybdène comme traceur des origines des concentrés miniers d’uranium. Cependant, un fractionnement des isotopes du molybdène a été établi lors de la production des concentrés miniers d’uranium pour deux usines au Niger. Les procédés de purification de l’uranium tels que la lixiviation, l’extraction par solvant et la précipitation ont été reproduits en laboratoire sur des échantillons réels pour expliquer le fractionnement isotopique du molybdène lors de la production des concentrés miniers. Au cours de ces procédés, le fractionnement peut être positif (lixiviation), négatif (extraction par solvant, précipitation à l’eau oxygénée) ou nul (précipitation à l’ammoniaque). Dans le cas des échantillons du Niger, la somme de ces procédés est négative, dans le sens des données expérimentales que nous avons obtenues, démontrant ainsi également le potentiel de l’utilisation des isotopes du molybdène comme traceur des procédés de transformations des matériaux du cycle du combustible nucléaire
Nuclear forensics aims at determining the age, provenance as well as industrial or storage history of uranium ores and uranium ore concentrates that are part of the nuclear fuel cycle. Several potential tracers have already been identified for this purpose. However, these tracers are not providing always unambiguous information. This study is focused on establishing Mo isotopes as a new tracer of uranium ore provenance and of ore processing for its application in nuclear forensics. Molybdenum and uranium share a number of common geochemical properties. In the nuclear fuel cycle, molybdenum is an impurity that is difficult to separate during uranium extraction and purification processes, while its concentration is required to be lower than some specification limits. We focused this study on the first part of the nuclear fuel cycle, from the uranium ores extraction to the production of uranium ore concentrates.We developed an enhanced separation method for Mo from a uranium-rich matrix (uranium ores, uranium minerals, uranium ore concentrates) in order to analyze the mass fractionation induced by processes typical of the nuclear fuel cycle. Molybdenum isotopic compositions in uranium ores depend of adsorption and precipitation processes. The δ98Mo values of sedimentary uranium ores is shifted to negative values relative to magmatic ores. This provides a means of distinguishing these types of uranium ores. Uranium ores concentrates produced from both uranium ore natures (magmatic and sedimentary) have Mo isotope compositions similar to the uranium ores. These results suggest that molybdenum isotopes have a strong potential of as a tracer for identifying the origin of the uranium ore concentrates. However, Mo isotopes fractionations were established during the production of uranium ore concentrates in the both Niger mills. We reproduced in laboratory the lixiviation, solvent extraction and precipitation processes to explain these observations. The Mo isotopes fractionation is positive for the lixiviation process, negative for the solvent extraction and precipitation with hydrogen peroxide, and null for ammonia precipitation. In the case of the Niger samples, the sum of these processes is negative and agrees with our experimental data. Mo isotopes have a strong potential as a tracer for identifying the origin and transformation of uranium in the nuclear fuel cycle, in the framework of nuclear forensics

abstract: Microbially induced calcium carbonate precipitation (MICP) is attracting increasing attention as a sustainable means of soil improvement. While there are several possible MICP mechanisms, microbial denitrification has the potential to become one of the preferred methods for MICP because complete denitrification does not produce toxic byproducts, readily occurs under anoxic conditions, and potentially has a greater carbonate yield per mole of organic electron donor than other MICP processes. Denitrification may be preferable to ureolytic hydrolysis, the MICP process explored most extensively to date, as the byproduct of denitrification is benign nitrogen gas, while the chemical pathways involved in hydrolytic ureolysis processes produce undesirable and potentially toxic byproducts such as ammonium (NH4+). This thesis focuses on bacterial denitrification and presents preliminary results of bench-scale laboratory experiments on denitrification as a candidate calcium carbonate precipitation mechanism. The bench-scale bioreactor and column tests, conducted using the facultative anaerobic bacterium Pseudomonas denitrificans, show that calcite can be precipitated from calcium-rich pore water using denitrification. Experiments also explore the potential for reducing environmental impacts and lowering costs associated with denitrification by reducing the total dissolved solids in the reactors and columns, optimizing the chemical matrix, and addressing the loss of free calcium in the form of calcium phosphate precipitate from the pore fluid. The potential for using MICP to sequester radionuclides and metal contaminants that are migrating in groundwater is also investigated. In the sequestration process, divalent cations and radionuclides are incorporated into the calcite structure via substitution, forming low-strontium calcium carbonate minerals that resist dissolution at a level similar to that of calcite. Work by others using the bacterium Sporosarcina pasteurii has suggested that in-situ sequestration of radionuclides and metal contaminants can be achieved through MICP via hydrolytic ureolysis. MICP through bacterial denitrification seems particularly promising as a means for sequestering radionuclides and metal contaminants in anoxic environments due to the anaerobic nature of the process and the ubiquity of denitrifying bacteria in the subsurface.
Dissertation/Thesis
M.S. Engineering 2013

abstract: The potential of using bio-geo-chemical processes for applications in geotechnical engineering has been widely explored in order to overcome the limitation of traditional ground improvement techniques. Biomineralization via urea hydrolysis, referred to as Microbial or Enzymatic Induced Carbonate Precipitation (MICP/EICP), has been shown to increase soil strength by stimulating precipitation of calcium carbonate minerals, bonding soil particles and filling the pores. Microbial Induced Desaturation and Precipitation (MIDP) via denitrification has also been studied for its potential to stabilize soils through mineral precipitation, but also through production of biogas, which can mitigate earthquake induced liquefaction by desaturation of the soil. Empirical relationships have been established, which relate the amount of products of these biochemical processes to the engineering properties of treated soils. However, these engineering properties may vary significantly depending on the biomineral and biogas formation mechanism and distribution patterns at pore-scale. This research focused on the pore-scale characterization of biomineral and biogas formations in porous media. The pore-scale characteristics of calcium carbonate precipitation via EICP and biogenic gas formation via MIDP were explored by visual observation in a transparent porous media using a microfluidic chip. For this purpose, an imaging system was designed and image processing algorithms were developed to analyze the experimental images and detect the nucleation and growth of precipitated minerals and formation and migration mechanisms of gas bubbles within the microfluidic chip. Statistical analysis was performed based on the processed images to assess the evolution of biomineral size distribution, the number of precipitated minerals and the porosity reduction in time. The resulting images from the biomineralization study were used in a numerical simulation to investigate the relation between the mineral distribution, porosity-permeability relationships and process efficiency. By comparing biogenic gas production with abiotic gas production experiments, it was found that the gas formation significantly affects the gas distribution and resulting degree of saturation. The experimental results and image analysis provide insight in the kinetics of the precipitation and gas formation processes and their resulting distribution and related engineering properties.
Dissertation/Thesis
Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2019

碩士
國立中正大學
應用地球物理研究所
99
Microbial carbonate precipitation (MCP) is a biologically-induced precipitation of calcium carbonate whereby microbial activities result in the generation of carbonate in a calcium rich environment. MCP has experienced an increased level of interest in recent years, for applications such soil reinforcement, strengthening of concrete, restoration of calcareous stone materials and bioremediation. Many biological reactions can result in the production of carbonate or carbonate species. Because of its simplicity and the lack of an excess proton production, the most commonly studied system of applied MCP to date is urea hydrolysis via the enzyme urease, in a calcium-rich environment. Carbonate ions produced, combine with calcium ions to produce calcium carbonate as follows: CO(NH2)2 + 2H2O → 2NH4+ + CO32− Ca2+ + CO32− → CaCO3 ↓ Besides soil reinforcemnt, some factors that needs to consider during MCP are the residual ammonium chloride and urea,which will affect the soil mass by providing toxicity which in turn will affect the soil properties. In order to improve the situation and reduce the cost of using urea during process of MCP, we focused our study by using limestone (CaO) and pig urine in the experiments. X-ray diffraction indicated that limestone and pig urine are very efficient in calcium carbonate precipitation with Aragonite percentage was a major carbonate form. We also use this method applied to soil liquefaction, and use vick trial observe the cementation.

The extraction and processing of uranium for use in the nuclear weapons program and in commercial nuclear energy has led to extensive contamination of the environment. Migration of uranium is also a concern for the proposed long-term nuclear waste disposal in geologic repositories. Reactions occurring at mineral surfaces significantly affect the mobility of uranium in the environment. Both the equilibrium and kinetics of reactions at mineral surfaces must be understood in order to predict the extent of reactions on time scales pertinent to human exposure. Such information is needed to establish input parameters for reactive transport models and to design remediation technologies. Rates of uranium sorption on mineral surfaces and the dissolution of uranium-containing minerals have been investigated. Rates of sorption onto and desorption from goethite, an important environmental sorbent, were determined by measuring the responses of goethite suspensions (pre-equilibrated with or without uranium) to perturbations of the solution chemistry. Dissolution rates were measured for a set of laboratory-synthesized minerals: the uranyl oxide hydrate schoepite, the uranyl silicate soddyite, and a uranyl phosphate phase. These minerals have been observed in contaminated environments and are produced during the corrosion of spent nuclear fuel. Mineral dissolution and transformation were monitored in batch reactors, while dissolution rates were quantified in flow-through reactors. In both sorption and dissolution-precipitation studies, measurements of bulk solution chemistry were integrated with solid phase characterization. While sorption processes were rapid, dissolution and surface-precipitation reactions occurred more slowly. Adsorption and desorption reactions of uranium onto or from goethite reached greater than 50% completion within minutes and completion on a time-scale of hours. In some uranium-goethite suspensions, a meta-stable sorption state persisted for as long as three weeks before a schoepite-like phase precipitated. Dissolution reactions proceeded at time-scales of hours for schoepite and days to weeks for soddyite and the uranyl phosphate. Common groundwater cations affected dissolution rates and, in several cases, resulted in the precipitation of uranium in secondary phases. In several schoepite and soddyite batch dissolution experiments, uranium ultimately reprecipitated in sodium or cesium uranyl oxide hydrate phases which subsequently controlled the dissolved uranium concentration.

In dieser Arbeit befassen wir uns mit einem reaktiven Transportmodell mit Niederschlags-Auflösung Reaktionen das aus den Geowissenschaften stammt. Es besteht aus PDGs, gewöhnlichen Differentialgleichungen, algebraischen Gleichungen und Komplementaritätsbedingungen. Nach Diskretisation dieses Modells erhalten wir eine großes nichtlineares und nichtglattes Gleichungssystem. Wir lösen dieses System mit der semismoothen Newtonverfahren, das von Qi und Sun eingeführt wurde. Der Fokus dieser Arbeit ist in der Anwendung und Konvergenz dieses Algorithmus. Wir zeigen, dass dieser Algorithmus für dieses Problem wohldefiniert ist und sogar lokal quadratisch konvergiert gegen eine BD-reguläre Lösung. Wir befassen uns auch mit den dabei entstehenden linearen Gleichungssystemen, die sehr groß und dünn besetzt sind, und wie sie effizient gelöst werden können. Ein wichtiger Bestandteil dieser Untersuchung ist die Beschränktheit einer gewissen matrixwertigen Funktion, die in einem eigenen Kapitel gezeigt wird. Als Seitenbetrachtung untersuchen wir wie die extremalen Eigenwerte (und Singulärwerte) von gewissen PDE-Operatoren, welche in unserem diskretisierten Modell vorkommen, genau abgeschätzt werden können
In this thesis we consider a reactive transport model with precipitation dissolution reactions from the geosciences. It consists of PDEs, ODEs, algebraic equations (AEs) and complementary conditions (CCs). After discretization of this model we get a huge nonlinear and nonsmooth equation system. We tackle this system with the semismooth Newton method introduced by Qi and Sun. The focus of this thesis is on the application and convergence of this algorithm. We proof that this algorithm is well defined for this problem and local even quadratic convergent for a BD-regular solution. We also deal with the arising linear equation systems, which are large and sparse, and how they can be solved efficiently. An integral part of this investigation is the boundedness of a certain matrix-valued function, which is shown in a separate chapter. As a side quest we study how extremal eigenvalues (and singular values) of certain PDE-operators, which are involved in our discretized model, can be estimated accurately

碩士
國立交通大學
環境工程所
91
The objective of this thesis is to investigate the influences of surface precipitation in a zero-valent iron on the permeable reactive barrier (PRB). The zero-valent iron (Fe0) is the most commonly used reactive material in the PRBs because it reacts with a variety of chlorinated aliphatic hydrocarbons (CAHs). The buildup of surface mineral precipitation when remediating TCE by PRB will decrease the porosity of reactive medium. In this study, the hydrologic character tics and the rate of precipitation at two contaminated sites in U.S. are employed to simulate the effect of corrosion of zero-valent iron. The principal factors that determine the amount of mineral precipitation and the spatial distribution of precipitates in a reactive iron media are flow rate, groundwater chemistry, and microbial community structure. As the result, there is no obvious evidence that the effect of porosity loss will reduce the capability of PRB.

Underground injection of acid gas has been studied for several decades for oil field applications, such as enhanced oil recovery (EOR), but is now being studied as a solution to climate change. This research aims to simulate underground conditions at injection sites, such as the pilot scale injection site located near the site of a coal fired power facility in the Black Warrior Basin of Alabama. This proposed carbon capture and sequestration (CCS) location would involve injection of liquid CO2 into a carbonaceous saline aquifer. The objective of this study was to investigate carbonate surface treatments that alter the kinetics and mechanism of mineral dissolution resulting from the injection of an acid gas (CO2) into a geologic formation. A variety of mineral coatings were tested in an attempt to preserve mineral integrity under acidic conditions. Surface active chemicals were first tested, including scale inhibitors, followed by a novel acid induced surface treatment that precipitates an inorganic layer on the calcite to preserve the acid soluble mineral. These experiments are the first to investigate the use of scale inhibitors for mineral preservation, although were found ultimately to have little impact on dissolution kinetics. However, anions of moderate to strong acids induced surface coatings that were determined to effectively inhibit dissolution. Additionally, a novel, high pressure flow-through experimental apparatus was developed to simulate pressure and temperature conditions relevant to injection sites. Similar mineralogical studies in the literature have used pressurized, unstirred, batch systems to simulate mineral interactions. Solids with an acid induced surface coating were tested in the high pressure column and no calcium was found to leave the column.

The overall objective of this research was to gain an insight into the challenges encountered during chemical flooding under high hardness conditions. Different aspects of this problem were studied using a combination of laboratory experiments and simulation studies. Chemical Flooding is an important Enhanced Oil Recovery process. One of the major components of the operational expenses of any chemical flooding project, especially Alkali Surfactant Polymer (ASP) flooding is the cost of softening the injection brine to prevent the precipitation of the carbonates of the calcium and magnesium ions which are invariably present in the formation brine. Novel hardness tolerant alkalis like sodium metaborate have been shown to perform well with brines of high salinity and hardness, thereby eliminating the need to soften the injection brine. The first part of this research was aimed at designing an optimal chemical flooding formulation for a reservoir having hard formation brine. Sodium metaborate was used as the alkali in the formulation with the hard brine. Under the experimental conditions, sodium metaborate was found to be inadequate in preventing precipitation in the ASP slug. Factors affecting the ability of sodium metaborate to sequester divalent ions, including its potential limitations under the experimental conditions were studied. The second part of this research studied the factors affecting the ability of novel alkali and chelating agents like sodium metaborate and tetrasodium EDTA to sequester divalent ions. Recent studies have shown that both these chemicals showed good performance in sequestering divalent ions under high hardness conditions. A study of the geochemical species in solution under different conditions was done using the computer program PHREEQC. Sensitivity studies about the effect of the presence of different solution species on the performance of these alkalis were done. The third part of this research focused on field scale mechanistic simulation studies of geochemical scaling during ASP flooding. This is one of the major challenges faced by the oil and gas industry and has been found to occur when sodium carbonate is used as the alkali and the formation brine present in situ has a sufficiently high hardness content. The multicomponent and multiphase compositional chemical flooding simulator, UTCHEM was used to determine the quantity and composition of the scales formed in the reservoir as well as the injection and production wells. Reactions occurring between the injected fluids, in situ fluids and the reservoir rocks were taken into consideration for this study. Sensitivity studies of the effect of key reservoir and process parameters like the physical dispersion and the alkali concentration on the extent of scaling were also done as a part of this study.
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Flow and transport phenomena in the subsurface often span a wide range of length (nanometers to kilometers) and time (nanoseconds to years) scales, and frequently arise in applications of CO₂ sequestration, pollutant transport, and near-well acid stimulation. Reliable field-scale predictions depend on our predictive capacity at each individual scale as well as our ability to accurately propagate information across scales. Pore-scale modeling (coupled with experiments) has assumed an important role in improving our fundamental understanding at the small scale, and is frequently used to inform/guide modeling efforts at larger scales. Among the various methods, there often exists a trade-off between computational efficiency/simplicity and accuracy. While high-resolution methods are very accurate, they are computationally limited to relatively small domains. Since macroscopic properties of a porous medium are statistically representative only when sample sizes are sufficiently large, simple and efficient pore-scale methods are more attractive. In this work, two Eulerian pore-network models for simulating single-phase flow and solute transport are developed. The models focus on capturing two key pore-level mechanisms: a) partial mixing within pores (large void volumes), and b) shear dispersion within throats (narrow constrictions connecting the pores), which are shown to have a substantial impact on transverse and longitudinal dispersion coefficients at the macro scale. The models are verified with high-resolution pore-scale methods and validated against micromodel experiments as well as experimental data from the literature. Studies regarding the significance of different pore-level mixing assumptions (perfect mixing vs. partial mixing) in disordered media, as well as the predictive capacity of network modeling as a whole for ordered media are conducted. A mortar domain decomposition framework is additionally developed, under which efficient and accurate simulations on even larger and highly heterogeneous pore-scale domains are feasible. The mortar methods are verified and parallel scalability is demonstrated. It is shown that they can be used as “hybrid” methods for coupling localized pore-scale inclusions to a surrounding continuum (when insufficient scale separation exists). The framework further permits multi-model simulations within the same computational domain. An application of the methods studying “emergent” behavior during calcite precipitation in the context of geologic CO₂ sequestration is provided.
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Thermal waters in Karlovy Vary are characterized by carbonate sedimentation in places of their emergence. These sediments contain radium. Radium bond in every type of sinter (aragonite, calcite) has been investigated experimentally by acid sinter dissolution. It has been found out, that radium can join dissoluble fraction in both sinter types . The original hypothesis that radium can bond only aragonite-type of sinter has been refuted. Additional experiments have been processed using synthetic radiobarite. Present radium in radiobarite can be partly dissoluted using acids. If radium was incorporated in radiobarite (it is known from locality Vřídlo in Karlovy Vary and elsewhere) then maybe it would be partly dissoluted in experiments.

碩士
國立中央大學
應用地質研究所
97
Investigation of chemical reactions between a fluid and the porous medium through which it flows, and of the subsequent changes in the medium porosity and hydraulic conductivity, is an area of interest for many scientific, industrial and engineering. Dissolution and precipitation are two of the most important processes affecting fluid chemistry, and they can significantly modify the physical and chemical properties of porous media. In this study, we investigate the effect of particle size of carbonate rock on temporal evolution of porosity and hydraulic conductivity induced by dissolution and precipitation by performing a series of laboratory surface reaction experiment and column flow experiment by injecting HCl/H2SO4. The temporal evolution of overall hydraulic conductivity is calculated by measurement of change in hydraulic head gradient and application of Darcy’s law. Variation in porosity is obtained by analyzing the effluent acid for Ca2+ and and invoking the law of mass balance. Furthermore, after each experiment, the column sample is retrieved and sectioned in order to study the micro-morphology and mineral composition. Results show that significant fluctuations in porosity and hydraulic conductivity occur due to competition between dissolution and precipitation. The patterns of fluctuations in porosity and hydraulic conductivity are influenced by particle size of calcium carbonate. SEM analysis shows that gypsum precipitates in the inlet of the column. These findings are in qualitative agreement with conceptual understanding of such phenomena.