Naturally occurring radioactive material (NORM) exists in connate waters and, under the right conditions during oil drilling, can plate out on the interior surfaces of oil and gas industry equipment. Once deposited, this material is commonly referred to as ??scale.?? This thesis is concerned with the presence of 226Ra in scale deposited on the inner surfaces of oil drilling pipes and the internal dose consequences of inhalation of that scale once released. In the process of normal operation, barium sulfate scale with a radium component adheres to the inside of downhole tubulars in oil fields. When crude flow is diminished below acceptable operational requirements, the pipe is sent to a descaling operation to be cleaned, most likely by a method known as rattling. The rattling process generates dust. This research investigated the chemical composition of that aerosol and measured the solubility of pipe scale from three oilfield formations. Using standard in-vitro dissolution experimental equipment and methods, pipe scale is introduced into simulated lung fluid over a two-week period. These samples are analyzed using quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS), known for very low detection limits. Analysis reveals virtually no 226Ra present in the lung fluid exposed to pipe scale. Sample measurements were compared against background measurements using Student??s t test, which revealed that nearly all the samples were statistically insignificant in comparison to the lung fluid blanks. This statistical test proves within a 95% confidence interval that there is no 226Ra present in the lung fluid samples. These results indicate that inhaled NORM pipe scale should be classified as Class S and serve to further confirm the extreme insolubility of petroleum pipe scale. For dose calculations, the S classification means that the lung is the main organ of concern. Radium-226 from petroleum pipe scale does not solubilize in the interstitial lung fluid, and does not, therefore, enter the bloodstream via respiratory pathways. Since there is no removal by dissolution, the 500 day biological half-life implied by the S classification is based solely on the mechanical transport of 226Ra out of the lungs by phagocytosis or the mucociliary escalator.

No description available.

The present study examines three non-marital, romantic relationship dissolution types: (1) normal dyadic dissolution, (2) fatal attraction dissolution, and (3) social allergen dissolution among a sample of 321 emerging adults, who are between ages eighteen and twenty-nine. Results of an online survey revealed that normal dyadic dissolution occurred in 62%, social allergen dissolution occurred in 27%, and fatal attraction dissolution occurred in 11% of the participants’ relational demises. Results also revealed that there is a surprising amount of overlap between the three dissolution types, and that age is not specifically correlated with a particular dissolution type. However, there are two predicators of dissolution type within an emerging adult population: perceived family support and whether or not the couple cohabitate.

No description available.

This study used petrographic thin sections, scanning electron microscopy, and confocal laser microscopy to document microbially mediated dissolution of carbonate reservoir rocks. The samples studied came from three carbonate units that are hydrocarbon reservoirs; the Salem, Sligo, and Smackover formations. These samples were inoculated with bacteria, and then treated with nutrient solutions followed by ethanol to promote generation of acetic acid by bacteria. Dissolution occurred in calcite-dominated rocks and in dolomitized rocks. Noticeable changes first occurred after nine weeks of ethanol treatment and significant change only occurred after twelve weeks of ethanol treatment. The size of the vuggy pores created increased from 1 µm or less to over 5 µm, and rarely over 10 µm, in length.

Dissolution experiments were conducted on bioapatite at 4°C, 21°C and 38°C and solution pH values between 2 and 8 in a stirred tank reactor. The bioapatite was obtained from modern white-tailed deer (Odocoileus virginianus) scapulae, crushed, and cleaned in 30% hydrogen peroxide to remove organic matter. The average BET specific surface area of the 75-106 and 106-246 μm particles was 255 m2 g-1. During experiments the ratio of Ca:P released became stoichiometric at ca. 1.44. The following dissolution rate law was derived from the experimental results: R = K1(H+)ⁿ+K2 in which R is the dissolution rate (mol bioapatite m-2 s-1) based on the bioapatite stoichiometry, n = 1.01 ± 0.15, k1 = 1.84 x 10-6 ± 1.71 x 10-6 mol m-2 s-1, and k2 = 4.29 x 10-10 ± 1.15 x 10-10 mol m-2 s-1 and H+ is the hydrogen ion activity. From 2 < pH < 4, dissolution rate is dependent on pH and becomes independent of pH from 4 < pH < 8. These results for modern bone may be compared with previous investigations of igneous (FAP) and phosphorite-derived sedimentary carbonate fluorapatites (CFA)(e.g., Guidry and Mackenzie, 2003). At pH = 6, in the pHindependent region, dissolution of the modern bioapatite was ca. 7 times faster than FAP and 100 times faster than CFA. The acid transition pH of the bioapatite (pH = 4) is lower than that for FAP (pH = 6). Bioapatite dissolution rates influence fossil preservation potential, the release rate of nutrients from bone meal fertilizers, the effectiveness of bone as reactive barriers to control pollutants and nuclear waste isolation, and as a feedstock material in CO2 sequestration processes. / Geology

Dans le cadre de l’utilisation potentielle d’oxydes mixtes d’actinides au sein des réacteurs nucléaires de 3ème et 4ème générations, des solutions solides de formules générales U1-xThxO2, U1-xCexO2-y, U0,75Nd0,25O1,875, U0,75Gd0,25O1,875 et Th0,75Nd0,25O1,875 ont été préparées par conversion thermique de précurseurs oxalate. Préalablement à l’évaluation de la durabilité chimique des matériaux, une étape de frittage a été entreprise afin d’obtenir des pastilles denses présentant diverses propriétés physico-chimiques et microstructurales d’intérêt (composition, homogénéité, taux de densification, …) L’étude multiparamétrique de la dissolution, conduite en milieux nitrique, sulfurique et chlorhydrique a souligné l’impact important de la composition chimique au sein du matériau sur la durabilité chimique des échantillons. En effet, plusieurs paramètres (ordres partiels par rapport à l’activité en protons, énergie d’activation apparente, …) ont confirmé une modification significative du mécanisme de dissolution prépondérant pour les échantillons enrichis en uranium. Par ailleurs, le rôle important joué par certaines espèces azotées à l’interface solide/solution a également été démontré. L’évolution de l’interface solide/solution (surface réactive, composition) en cours de dissolution a également été suivie à travers une étude operando par Microscopie Electronique à Balayage en mode Environnemental. Cette étude a souligné l’existence de zones préférentielles de dissolution (jonctions triples, joints de grains, porosités inter- et intragranulaires) pour les échantillons les moins riches en uranium ; laquelle s’accompagne d’une forte augmentation de la surface réactive. En raison d’un phénomène prépondérant d’oxydation de l’uranium(IV) à l’interface, la dissolution des échantillons enrichis en uranium apparaît nettement plus homogène. / In the field of the use of actinides mixed oxides as potential fuels for the Gen(III) and Gen(IV) nuclear reactors, solid solutions with general formula U1-xThxO2, U1-xCexO2-y, U0.75Nd0.25O1.875, U0.75Gd0.25O1.875 and Th0.75Nd0.25O1.875 were prepared by thermal conversion of oxalate precursors. Dense pellets exhibiting various physico-chemical and microstructural properties (in terms of composition, homogeneity, densification rate, …) were prepared through sintering then submitted to dissolution tests.The multiparametric study of the dissolution, performed in nitric, sulfuric and hydrochloric media clearly underlined the important effect of the chemical composition on the chemical durability of the samples. Indeed, several parameters (including partial order related to proton activity, apparent activation energy) confirmed the significant modification of the preponderant dissolution mechanism for uranium-enriched samples. Moreover, the role of various nitrogen-based species was evidenced at the solid/solution interface.The evolving of solid/solution interfaces (reactive surface area, composition) during dissolution was monitored by the means of operando ESEM experiments. Preferential dissolution zones (triple junctions, grain boundaries, inter- and intra-granular porosities) were clearly observed for uranium-depleted samples. They induce a significant increase of the reactive surface area even for short progress of the reaction. On the contrary, the dissolution appeared more homogenous for uranium-enriched samples due to the existence of a preponderant mechanism associated to the oxidation of the uranium(IV) at the interface.

Dans le cadre de la loi programme relative à la gestion durable des matières et déchets radioactifs du 28 Juin 2006, la France a choisi comme solution de référence le retraitement de ses combustibles usés et le stockage en milieu géologique profond des déchets ultimes vitrifiés. Néanmoins, les études relatives à un stockage direct des combustibles usés se poursuivent par mesure de précaution. Le concept de stockage prévoit de conditionner les assemblages de combustibles usés dans un surconteneur en acier dont l'étanchéité est garantie sur une durée spécifiée de l'ordre de 10 000 ans. L'arrivée d'eau au contact du combustible après dégradation du conteneur initie les processus de dégradation de la matrice UO2 conduisant au relâchement des radionucléides. Il est de ce fait, important de connaître et de comprendre le mécanisme d’altération de la matrice UO2. Pour cela, des techniques électrochimiques (voltammétries cyclique et linéaire) couplées à des techniques de caractérisation du solide et de la solution (XPS, ICP-MS) ont été utilisées.Une étude thermodynamique et bibliographique du système U(VI)/UO2(s) a permis de mettre en évidence l’influence des conditions physico-chimiques de la solution sur le système, et de mettre en évidence les différents mécanismes proposés pour décrire l’oxydation/dissolution d’UO2 dans différents milieux (non-complexant, carbonaté et argileux). L’étude de l’oxydation/dissolution d’UO2 en milieu acide non-complexant (NaCF3SO3 0,1 mol/L à pH = 3), milieu où le couple UO22+/UO2 prédomine et où la formation de précipités est limitée voire évitée, a mis en évidence un mécanisme en deux étapes électrochimiques et un modèle caractéristique de l’oxydation d’UO2 en milieu acide non-complexant. Ensuite, l’étude en milieu neutre non-complexant (NaCl 0,05 mol/L à pH = 7,5) a mis en évidence un mécanisme en deux étapes électrochimiques et une étape chimique (EEC) dans lequel les deux étapes électrochimiques sont similaires à celles proposées en milieu acide. Enfin, une première approche de l’oxydation/dissolution d’UO2 a été réalisée en milieu carbonaté (NaCl 0,05 mol/L + NaHCO3 2.10-3 mol/L à pH = 7,5) puis en présence d’une phase argileuse (MX80) dans la solution d’étude. Ces études ont respectivement montré l’influence des carbonates et de la MX80 sur la dissolution du dioxyde d’uranium. / Within the framework of the geological disposal of spent nuclear fuel, research on the long term behavior of spent fuel is undertaken and in particular the study of mechanisms of UO2 oxidation and dissolution in water-saturated host rock. Under the law program on the sustainable management of radioactive materials and waste of June 28, 2006, France was chose as the reference solution the retreatment of spent fuel and disposal in deep geological repository of vitrified final waste. Nevertheless, studies on a direct disposal of spent fuel will continue for safety. The disposal concept provides for conditioning spent fuel in a steel container whose seal is guaranteed for a period specified in the order of 10,000 years. It is also reasonable to assume that the groundwater comes into contact with the fuel after the deterioration of container and lead to the UO2 matrix degradation and the release of radionuclides. The oxidation/dissolution of UO2 has been studied by means electrochemical methods coupled to XPS and ICP-MS measurements.A thermodynamic and bibliographic study of U(VI)/UO2(s) system allowed to show the effect of the physical and chemical conditions of the solution on the system, and to show the different mechanisms proposed to describe the oxidation and the dissolution of the uranium dioxide in different media (non-complexing, carbonate and clay). The study of the oxidation/dissolution of UO2 in acidic and non-complexing media (0.1 mol/L NaCF3SO3, pH = 3), where UO22+/UO2(s) predominates and the formation of precipitates is limited or even avoided, showed a mechanism with two electrochemical steps and a model characteristic of UO2 oxidation in acidic non-complexing media. Then, the study in neutral non-complexing media (0.05 mol/L NaCl, pH = 7.5) showed a mechanism with two electrochemical steps and one chemical step (EEC) in which both electrochemical steps are similar to those proposed in acidic media. Finally, a first approach of the UO2 oxidation/dissolution was carried out in carbonate media (0.05 mol/L NaCl + 2x10-3 mol/L NaHCO3, pH = 7.5) and in the presence of clay (MX80) in the solution. These studies have respectively shown the influence of carbonates and MX80 on the dissolution of uranium dioxide.

The weathering of apatite is the foundation of the phosphorus cycle and essential to life, yet little is known about the nanoscale mechanisms driving apatite weathering. Deciphering nanoscale dissolution in apatite is a significant step to understand phosphate weathering behavior, that was key to the development of life. Determining what controls apatite weathering can impact many areas of environmental and medical mineralogy such as dentistry, contaminant scavenging, geochronology, and paleoenvironment studies. The aim of this study was to characterize apatite dissolution across scales with an emphasis on the nanoscale mechanisms. Recent research on the weathering of silicate minerals at the nanoscale has provided telling evidence of a relatively new chemical weathering model referred to as coupled interfacial dissolution-precipitation (CIDR) mechanism. We hypothesize that this mechanism could be broadened to phosphate minerals. To investigate crystals of Durango fluorapatite (FAP) and hydroxyl-chlorapatite (HAP) were hydrolyzed in flow-through devices with pH 3 HNO3 solutions. Apatites used in the study were chemically and structurally characterized via Single Crystal-XRD, with particular emphasis on the anion composition and atomic arrangement. Determination of the mechanisms of dissolution was carried at multiple scales using ICP-OES chemical analysis (macroscale), SEM (microscale) and STEM-HAADF-EDS/EELS on FIB liftouts (nanoscale). At the macroscale, The anionic composition of the apatite controlled its weathering rate. As expected, HAP dissolution occurred at faster rates compared to FAP. SEM characterization of the crystal surfaces pre- and post-dissolution revealed the development of etch pits during dissolution, however, more pronounced for FAP than HAP. Observation of the mineral/solution interface at the nanoscale using STEM-HAADF revealed the development of a nanometric amorphous layer likely depleted in Ca compared to P. The observation of a sharp crystalline/amorphous transition and 5 to 15 nanometers thick amorphous surface altered layer, associated with a depletion in Ca suggests that similar to silicate, apatite is subject to a coupled interfacial dissolution-reprecipitation mechanism. This potential discovery could transform our understanding of phosphate behavior in medical and environmental mineralogy fields.

Mineral dissolution is an inherent chemo-hydro-mechanical coupled diagenetic process in sediments. This ubiquitous geological phenomenon affects all properties in sediments, however, its engineering impact remains largely unknown. This research centers on the effects of mineral dissolution on sediment behavior with emphasis on dissolution modes in nature and their engineering implications. Five different dissolution modes are identified: homogeneous, pressure-dependent, and localized dissolution, and the dissolution of shallow and deep dissolvable inclusions. The consequences of each dissolution mode are investigated through experiments and discrete element methods. While each dissolution mode triggers unique consequences, it is observed that in all cases 1) significant displacement takes places during dissolution, 2) there is a pronounced effect of internal friction and the extent of dissolution on the evolution of the sediment, 3) the sediment has higher compressibility and exhibits a more contractive tendency after dissolution, 4) a porous honeycomb-shaped internal fabric develops accompanied by contact force concentration along dissolved inclusions, and 5) horizontal stress reduction takes place during dissolution and shear localization may develop under zero lateral strain conditions. Mineral dissolution has important engineering implications, from soil characterization to slope stability and shallow foundations. Pre- and post-dissolution CPT studies show that dissolution decreases the tip resistance proportional to the extent of dissolution. Dissolution in sloping ground induces global settlement as the prevailing deformation pattern, and prominent lateral movements near the slope surface; sudden undrained shear failure may take place during otherwise quasi-static dissolution. While footings experience larger settlements during post-dissolution loading, subsequent dissolution beneath a previously loaded footing causes displacements that are greater than the sum of dissolution-induced and load-induced settlements.