Mn is a geochemically important element that contributes significantly to the cycling of heavy metals. During precipitation, Mn oxyhydroxides scavenge many heavy metals, including Pb, in a variety of natural environments. Because of this phenomenon, the precipitation of Mn oxyhydroxides may provide a remediation technique for removing Pb from contaminated aqueous solutions. Therefore, this study was undertaken to provide a quantitative understanding of the coprecipitation of Pb with Mn oxyhydroxides to demonstrate their capacity to remove Pb permanently from contaminated solutions. To accomplish this, a series of factorial experiments with varying initial Mn and Pb concentrations were run in the presence of a borate buffer or a bicarbonate buffer. All experiments were run in batch reactors, in the presence of a quartz substrate, at 25 degrees celcius, at pH 8.5, and were continuously stirred. Initial Mn and Pb concentrations were varied by half log units from 100 to 0 mg/L and from 3 to 0 mg/L, respectively. Solutions were analyzed for Mn using the formaldioxime colorimetric method and for Pb using AA. Precipitates on quartz surfaces were analyzed by SEM, XPS, and XRD for precipitate identification and morphology. The amount of Mn and Pb associated with the quartz sand was determined by dissolving the precipitates from selected quartz samples using concentrated nitric acid. Finally, a different set of precipitate-coated quartz grains were leached in pH 5 acetic acid solution to assess the metal retention capacity of the precipitated material. Mn oxyhydroxides precipitated onto the quartz sand in both the borate and bicarbonate buffered experiments. SEM and XPS data revealed tiny crystallites in etch pits on the quartz surfaces that contained predominantly Mn3+. XRD analysis did not produce an X-ray pattern for these Mn oxyhydroxides but did identify the suspended Pb precipitates as hydrocerrusite and Pb(HBO3)2 in the borate buffered experiments and hydrocerrusite in the bicarbonate buffered experiments. Much more Mn and Pb are associated with the quartz surfaces in the borate buffered experiments, but no Pb was associated with quartz surfaces initially (< 6 hrs. of reaction time). Leaching of precipitates resulted in extracted Mn in both experiments but Pb was extracted in only the bicarbonate buffered experiments. The Mn precipitation rate was greater in the borate buffered experiments and higher initial Mn and Pb concentrations appear to increase the precipitation rate in both sets of experiments. These results indicate that Mn oxyhydroxides nucleated onto suspended Pb precipitates. The growing Mn oxyhydroxide particles were attracted to the quartz sand, carrying along the Pb precipitates. Further precipitation of Mn oxyhydroxides on the quartz surfaces trapped the Pb. This process was much more significant in the borate buffered experiments where much more Mn precipitated. The greater amount of Mn oxyhydroxide growth acts as a barrier protecting the Pb from the pH 5 leaching solutions. As a result, Pb was retained by the sand grains from the borate buffered experiments during leaching while significant amounts of Pb (35-100%) was extracted from the sand produced by the bicarbonate experiments. These results strongly suggest that coprecipitation of Pb with Mn oxyhydroxides in the presence of a borate buffer and a quartz substrate may be a remediation tool for Pb contaminated aqueous solutions. Not only will this process remove aqueous Pb2+ from solution but it appears it will also substantially incorporate colloidal Pb particles as well. / Master of Science

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La synthèse de particules d'oxydes mixtes en solution aqueuse est souvent difficile à contrôler en raison de la réactivité potentiellement différente des espèces qui coprécipitent. L’objectif de la thèse est de tenter de comprendre et piloter la synthèse dans le cas du système de particules d’oxydes mixtes de titane et d'étain, choisi en raison de l'existence d'une solution solide sur toute la gamme de composition et de la possibilité de recourir à une précipitation homogène plus simple à modéliser que le mélange réactif. Les synthèses sont réalisées par thermohydrolyse avec chauffage micro-ondes de solutions acides, fournissant des particules directement cristallisées avec des temps de réaction réduits. Les résultats des synthèses, à savoir le rendement et la composition du solide, sont modélisés par un calcul de sursaturation nécessitant la connaissance de la spéciation des solutions préparées. Cette dernière est calculée par la détermination à la température de thermohydrolyse des constantes d’équilibres en solution à partir de données bibliographiques et de mesures de solubilité à basse température d'une part et d'autre part de modélisation de la dépendance thermique des grandeurs thermodynamiques. Enfin, des nanocomposites Anatase-Rutile ont été obtenus par coprécipitation de titane avec de petites quantité d’étain et les propriétés photocatalytiques de ces nanoparticules ont été testées. / The synthesis of mixed oxide particles in aqueous solution is often difficult to control because of the potentially different reactivity of coprecipitating species. The aim of the thesis is to try to understand and control the synthesis in the case of mixed titanium oxide particles and tin system, chosen because of the existence of a solid solution over the entire range composition and the possibility of using a simpler homogeneous precipitation to model the reactant mixture. The syntheses are carried out by thermal hydrolysis of acidic solutions with microwave heating, providing particles directly crystallized with reduced reaction times. The results of the synthesis, namely the yield and composition of the solid, are modeled by a calculation of the supersaturation requiring knowledge of the speciation of the prepared solutions. This is calculated by determining the temperature of thermal hydrolysis in solution equilibrium constants from bibliographic data and low-temperature solubility measurements on the one hand and on the other hand, modeling of the temperature dependence of the thermodynamic. Finally, Anatase-Rutile nanocomposites were obtained by coprecipitation of titanium with small amounts of tin and the photocatalytic properties of these nanoparticles were tested

The Enhanced Actinide Removal Plant (EARP) located at Sellafield, is a key facility for processing nuclear effluents in the UK. The EARP process decontaminates radioactive waste effluent by inducing the coprecipitation of Fe(III) along with any radionuclides in solution. The resulting radioactive solid phase is then separated from the decontaminated aqueous phase by ultrafiltration processes over several weeks. In the future the EARP facility's role will be expanded to treat effluents produced from nuclear decommissioning activities. However there remains a limited understanding around the mechanisms of radionuclide removal from solution and subsequent sequestration within the solid phase under conditions relevant to such industrial effluent treatment facilities. In this work, the fate of U(VI) and Th(IV) were investigated during the EARP process. XRD and TEM analyses revealed that the solid product from the EARP coprecipitation process was 2-line ferrihydrite which transformed over time to form hematite, with some goethite formation observed in the Th containing system. During this coprecipitation process U was initially removed from solution by adsorption to ferrihydrite as a bidentate, edge-sharing surface complex associated with ternary carbonate complexes. As the U containing system was aged, a maximum range of 61 - 75% U became consistently incorporated within the newly formed hematite phase for a wide range of systems containing 6 orders of magnitude total U:Fe molar ratio. Such a constant proportion of incorporated U suggests that this incorporation occurs during a particle mediated mechanism of hematite growth, such as oriented attachment. Interestingly, Th was removed from solution during the EARP coprecipitation process by a combination of both adsorption and occlusion mechanisms. EXAFS analyses revealed that the local coordination environment of Th associated with the solid phase altered considerably with increased aging time, and correspondingly Th became increasingly recalcitrant to remobilisation over time suggesting the formation of further occluded or even incorporated Th species within the transforming iron (oxyhydr)oxide phases. This thesis progresses the fundamental understanding of radionuclide interactions with iron (oxyhydr)oxide phases during coprecipitation and aging processes under conditions relevant to industrial waste treatment processes such as EARP.

Monitoring of Bear Lake was conducted in 1981 and 1982 to describe the current limnology and trophic state of the lake. The nutrientt loadings of various parameters were measured from April, 1981 through June, 1982. The rate of coprecipitation of phosphorus was determined for different initial phosphorus concentrations by use of non-algal assays. Algal bioassays with Selenastrum capricornutum were used to determine the reduction in potential algal biomass as a result of the coprecipitation of phosphorus. The lake exhibit-.ed chemical characteristics indicative of mesotrophy or eutrophy. Total phosphorus values averaged 11μg/1 for 1981 and 20 μg/1 for 1982. A hypolimnetic accumulation of phosphorus was also not:ed for the stratified periods. Addittionally, hypolimnetic oxygen deficit values were indicative of mesotrophy in 1981 and eutrophy in 1982. The chlorophyll concentrations were characteristic of oligotrophic conditions during both years however. Phosphorus was found to be limiting production approximately 85% of the year. The Bear River Contributed approximately 60% of the total phosphorus loading to the lake in 1981 and 50% in 1982. Overall, the total phophorus loading increased 195% between the dry year, 1981, and the wet year, 1982. Vollenweider's (1976) phosphorus loading model described the loading to Bear Lake as indicative of mesotrophic conditions in 1981 and eutrophic conditions in 1982. Calcium and magnesium concentrations fluctuated widely throughout the year. The Mg:Ca molar ratio varied from 1:1 in the spring to 3.5:1 in the fall. Total hardness values did not vary in response to the changing ionic concentrations and this was attributed to preferential replacement of precipitated calcium by the Bear River inflow. Non-algal assays quantified the removal of phosphorus by coprecipitation at increasing initial phosphorus by concentration. The rate of removal initial decreased substantially as phosphorus levels increased with a shift in reaction order from second order to first order noted at approximately 50 μg/1. Predictive models were derived from the initial assays and verified with data from a separate experiment which use filtered Bear Lake water. The models accurately predicted the amount of phosphorus removed by coprecipitation at all phosphorus levels. Algal bioassays in synthetic Bear Lake and soft-water media were used to evaluate the efficiency of the coprecipitation mechanism when in competition with algae for phosphorus. An average reduction in biomass of 40% was noted between the media at similar nutrient levels.

Abstract Ammonia (NH3) is one of valuable chemicals which is commonly used in manufacturing the fertilizer, synthetic fiber, synthetic plastics, and dynamites, and is used in the factories such as papermaking, textile mill, camera and electrical. NH3 is also a typical pollutant which is found to be emitted from industrial processes, agriculture areas and livestock farm. It causes burn damage due to the corrosion and has a long-term impact on human bronchus. This study was to investigate the performance and kinetics in oxidation of ammonia by using a method of selective catalytic oxidation (denoted by SCO) over a series catalysts of Cu/Ce . The major parameters were performed at the following conditions: initial concentration NH3 of influent in ranging from 500 ppm to 1000 ppm, temperatures ranging from 150¢J to 500¢J, oxygen content in inlet stream in ranging from 4¢Hto 20¢Hand humidity in ranging from 1¢Hto 20¢H(or an absolute humidity of 607 ppm-12136 ppm). In the first stage experiments, the purpose was to select a best catalyst, which had the great activity and highest selectivity on nitrogen. The catalysts used in this work were prepared into three types in the following: Cu/La/Ce (molar ratio: 8/1/1, 7/1/2, 7/2/1, 6/1/3, 6/2/2 and 6/3/1), Cu/La (molar ratio: 6/4, 7/3, 8/2 and 9/1) and Cu/Ce (molar ratio: 6/4, 7/3, 8/2 and 9/1); total numbers of catalysts were 14. Test results showed the molar ratio 6:4 of Cu/Ce catalyst was found to have the best activity and selectivity to convert NH3 in this work. The second stage experiments were carried to investigate the effect of parameters on conversion of NH3 over a Cu/Ce catalyst of molar ratio 6:4. The conversion of NH3 in process of SCO increased with operation conditions such as the going up of temperature, and the increasing both of oxygen content and of residence time. The lower conversion of NH3 was achieved by an increasing on initial concentration of NH3, space velocity and humidity. The third stage experiments were conducted to investigate the effect of operation period on deactivation of NH3 over the above catalyst. At constant initial concentration of NH3, oxygen content and space velocity for 30 hr continuously, we found Cu/Ce catalyst had an excellent stability in conversion of NH3. Further tests by XRD, SEM and EA were determined. The kinetics of SCO over a Cu/Ce catalyst of molar ratio 6:4 in oxidation of NH3, using differential method, was found that a pseudo-first order reaction could be described by Mars-Van Krevelend model. An equation of destruction efficiency in terms of NH3 was obtained, and a good fitting was got between the predicted and the experimental values.

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