<p>Coal fired power plants are ubiquitous in the United States and most developed countries around the world, providing affordable electricity to consumers. In the US, approximately six hundred power plants generate 136 million tons of Coal Combustion Residuals (CCRs) annually, encompassing fly ash, bottom ash, and flue gas desulfurization materials. The range and blends of CCRs varies substantially across coal-fired plants and depends on a unique set of circumstances for each plant and coal source. Current U.S. regulations mandate the installation of advanced capture technologies to reduce atmospheric pollution, but do not address the transfer and storage, or the potential impacts to water resources. Thus improved air quality is traded for significant enrichments of contaminants in the solid waste and effluent discharged from power plants. </p><p>This work examines the geochemical and isotopic characteristics of CCRs, as well as potential environmental impacts from CCRs. This investigation looks at several different aspects of CCR and environmental interactions from 1) the immediate impacts of the 2008 TVA coal ash spill in Kingston, TN, 2) the long-term (18-month) exposure of the spilled ash in the Emory and Clinch rivers, 3) impacts on waterways in North Carolina that receive CCR effluent from coal fired power plants, and 4) examination of boron and strontium isotopes of CCRs from leaching experiments and their application as tracers in the environment of the TVA spill and NC waterways. These investigations have illuminated several conclusions, including contact of surface water with CCRs leach high concentrations of leachable CCR contaminants, such as As, Se, B, Sr, Mo, and V in the surface waters; the dilution effect is critical in determining the concentration of contaminants from the CCRs in surface water (both at the spill and in waterways receiving CCR effluent); recycling of trace elements (such as As) through adsorption/desorption can impact water quality; and elevated boron and strontium concentrations, in addition to their isotopes, can trace CCR effluent in the environment. Combining the geochemical behavior and isotopic characteristics provides a novel tool for the identification CCR effluents in the environment.</p> / Dissertation

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abstract: This project investigates social mobility in premodern states through a contextualized program of isotopic research at the archaeological site of Teotihuacan, Mexico. Due to the lack of a concrete methodology that can be used to recover information concerning rates of social mobility from archaeological remains, many traditional archaeological models either ignore social mobility or assume that boundaries between socioeconomic strata within archaic states were largely impermeable. In this research, I develop a new methodological approach to the identification of socially mobile individuals in the archaeological record based on changes in the diet across the lifecourse that can be detected through isotopic paleodietary indicators. Drawing upon cross-cultural research surrounding the relationship between diet and socioeconomic status and established methodologies in the biogeochemical analysis of human remains, this methodological approach provides a basis for broader comparative studies evaluating the nature of social mobility within archaic states. I then test the practical application of this methodology by applying it to a mortuary sample including individuals from distinctive socioeconomic groups from the pre-Hispanic city of Teotihuacan, Mexico. The study recovers and uses the dietary isotope ratios within bone and tooth samples from 81 individuals buried throughout the city 1) to define the dietary correlates of wealth and status at Teotihuacan and 2) to identify individuals displaying lifetime dietary changes consistent with changes in socioeconomic status. In addition to supplementing our current understanding of Teotihuacan foodways and processes of geographic migration into the city, I identify an adult male individual from the La Ventilla B apartment compound who displays dietary changes throughout his life that are consistent with downward socioeconomic mobility from a high status socioeconomic group in early adolescence to an intermediate status group later in adulthood. I conclude by identifying ways to move forward with the comparative archaeology of socioeconomic mobility in premodern contexts and highlight the applicability of archaeological information to our understanding of present-day processes of social mobility. / Dissertation/Thesis / Doctoral Dissertation Anthropology 2017

abstract: Growth of the Phoenix metropolitan area led to exposures of the internal bedrock structure of surrounding semi-arid mountain ranges as housing platforms or road cuts. Such exposures in the Sonoran and Mojave deserts reveal the presence of sedimentary calcium carbonate infilling the pre-existing fracture matrix of the bedrock. Field surveys of bedrock fractures filled with carbonate (BFFC) reveal an average of 0.079 +/- 0.024 mT C/m2 stored in the upper 2 m of analyzed bedrock exposures. Back-scattered electron microscopy images indicate the presence of carbonate at the micron scale, not included in this estimation. Analysis of the spatial extent of bedrock landforms in arid and semi-arid regions worldwide suggests that ~1485 GtC could potentially be stored in the upper 2 m horizon of BFFCs. Radiocarbon dating obtained at one of the sites indicates it is likely that some of the carbonate was flushed into the bedrock system during glacial wet pulses, and is stored on Pleistocene timescales or longer. Strontium isotope analysis at the same site suggest the potential for a substantial cation contribution from weathering of the local bedrock, indicating the potential exists for sequestration of atmospheric carbon in BFFCs. Rates of carbon release from BFFCs are tied to rates of erosion of bedrock ranges in desert climates. / Dissertation/Thesis / M.A. Geography 2013

In this work, I present a multi-isotopic study (carbon, nitrogen, sulfur, strontium and lead) and Re-Os geochronology in rocks and crude oils of the Sonda de Campeche Petroleum System (SCPS). Since crude oils are complicated chemical systems easily disturbed, the Re-Os isotopic system could be affected if secondary processes perturb crude oils. Therefore, the multi stable isotopic study allows the identification of the presence and grade of these secondary processes in crude oils. The δ13C values of crude oils from the SCPS distinguish between: 1) crude oils with the fingerprint of source rocks of hydrocarbons (-28.3 to -26.7 ‰), and 2) crude oils with the fingerprint of the reservoir rocks (-25.5 to -24.9 ‰). Similarly, the δ15N values reveal that crude oils, during migration or trapping processes mimic the isotopic composition of the reservoir rocks of the Ek-Balam Formation. Furthermore, the δ34S values of crude oils from the SCPS (-8.0 to -2.5 ‰) show an absence of a thermal sulfate reduction (TSR) signature, which likely means that the use of Re-Os systematics in crude oils and rocks in the SCPS is appropriate. Strontium and lead measurements show crude oils have an isotopic composition different from rocks from the Edzna Formation but similar to rocks of the Akimpech and Ek-Balam formations, indicating that crude oils received Sr and Pb from the trapping rocks during migration or trapping processes, producing a isotopic mixing trend with rocks of these formations. Specifically, the lead isotope composition allows the identification of a source of lead never recorded before, the Guichicovi Complex. The isotopic data suggest that this Grenville Complex has been feeding with detrital material to the sedimentary rocks from Bacab, Ek-Balam and Akimpech formations in the SCPS, and in consequence contributing to the final isotopic composition of crude oils as well. Re-Os geochronology of rocks from the Edzna and Akimpech formations (152 ± 4 Ma; and 158.6 ± 5.5 Ma, respectively) provides precise ages of deposition that coincide with the ages proposed in previous studies based on the fossil record. Re-Os geochronology in crude oils yield ages with low uncertainty and moderate MSWD values, reflecting a rapid formation and migration process that occurred during evolution of the SCPS. The age of crude oils (28.3 ± 5.5 Ma) broadly agrees with petroleum generation models proposed by PEMEX.

M.Sc. / The strontium isotope ratio 87Sr/86Sr in the wine and soil of four wine-producing regions in South Africa has been determined using quadrupole ICP-MS. Isotope ratio measurements with fairly good precision had been obtained and 87Sr/86Sr ratio values in wine and soil samples were statistically evaluated to determine whether the regions investigated could be distinguished. Statistical interpretation of data revealed that the Robertson wine-producing region could be distinguished from Stellenbosch, Swartland and Walker Bay wine regions on the basis of their 87Sr/86Sr ratio. By using a combination of 87Sr/86Sr and multielement data, canonical discriminant functions with very good classification abilities could be obtained to correctly distinguish between wine and soil samples originating from a specific production region. Due to the isobaric overlap of strontium and rubidium at mass 87, a very good strontium-rubidium separation method had to be developed. The chelating properties of EDTA and DCTA in combination with ion exchange chromatography were explored in order to achieve such a separation. Due to the advanced rubidium separation ability of the developed DCTA elution method, it has been employed in all wine and soil sample preparations. Since chromatographic ion exchange procedures are not capable of removing all the rubidium from the sample matrices, 87Sr/86Sr ratio values were mathematically corrected for residual rubidium using an 88Sr correction. Since strontium isotope ratio measurements require very good precision, it is traditionally determined using TIMS. However, due to the ease of operation, shorter analysis time and widespread availability of quadrupole ICP-MS, the technique was evaluated for its merit for determining strontium isotope ratios. The optimization of acquisition parameters for the determination of the 87Sr/86Sr ratio in wine and soil samples with good precision of below 0.1% RSD has been conducted. Furthermore, selected sample matrix components were assessed as possible matrix interferences as well as for their ability to affect the precision of measurements. It was concluded that with adequate optimization of acquisition parameters, proper sample preparation and reliable mathematical correction of data, 87Sr/86Sr ratio measurements with reasonable precision could be obtained using quadrupole ICP-MS.

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Airborne particulate matter (PM) in urban areas is derived from a combination of natural and anthropogenic sources. To identify PM sources and their effects on air quality, we collected PM using active filter samplers over a two-year period in the urban Wasatch Front, northern Utah, an area affected by multiple pollution sources. Filters from active samplers and other PM samples were analyzed for major and trace element concentrations and 87Sr/86Sr ratios. We identified wind-blown mineral dust from dry lake beds, winter inversions, and fireworks as primary PM sources affecting air quality in the Wasatch Front. Dust contributes Al, Be, Ca, Co, Cs, Fe, Li, Mg, Mn, Rb, Th, U, Y, and REEs which are typical components of carbonate and silicate minerals. Winter inversions entrap As, Cd, Mo, Pb, Sb, Tl, and Zn from brake dust, combustion engine exhaust, and refining processes. Concentrations of common components of fireworks Ba, Cu, K, and Sr greatly increase (>4 times) during holidays. Strontium released from fireworks has a distinct 87Sr/86Sr ratio that dominates the isotopic composition of PM during holidays. Fireworks have 87Sr/86Sr ratios of <0.7080 compared with 0.7100 for Sevier Dry Lake and 0.7150 for Great Salt Lake lakebed. Sources of particulate matter vary seasonally. Dust events dominate the air quality signature during spring and summer while winter inversions occur from November through February. Transport of PM to mountain snowpack negatively affect water quality. This is the first study to describe variations in multiple PM sources and their potential health effects in Utah, USA

Le présent travail porte sur le développement technologique pour déterminer l'âge des sources de radiostrontium à travers du rapport [Zr-90]/[Sr-90], en utilisant les techniques de spectrométrie de masse et scintillation liquide pour quantifier les deux isotopes. Parce que Sr-90 et Zr-90 sont des interférences isobariques en spectrométrie de masse, une séparation radiochimique est nécessaire pour isoler du Zr-90 avant son analyse. Parmi quatre résines commerciales, la résine DGA a fourni la meilleure performance pour isoler le Zr-90 du Sr-90. Des récupérations supérieures à 99% pour le Zr-90 ont été obtenues. La résine DGA était aussi l'approche la plus rapide et la plus efficace pour éliminer les interférences isobariques du Sr-90 et aussi de l’Y-90 potentiellement présents dans des échantillons contenant des niveaux élevés de radioactivité. Des expériences impliquant l’utilisation d’une cellule de collision pour éliminer des interférences isobariques ont fourni des facteurs de décontamination insuffisants pour des applications en criminalistique nucléaire. / In this work, a technological development to determine the age of radioactive strontium sources through the [Zr-90]/[Sr-90] ratio using mass spectrometry and liquid scintillation to quantify both isotopes is presented. Because Sr-90 and Zr-90 are isobaric interferences in mass spectrometry, a radiochemical separation to isolate Zr-90 has been shown to be mandatory prior to analysis. Four commercial resins (AG50W-X9, Dowex1-X8, Sr and DGA resins) were tested to isolate Zr-90 from Sr-90. Best performance was observed for the DGA resin, including recoveries higher than 99% for Zr-90. DGA has also demonstrated to be the faster approach and the most efficient not only to eliminate isobaric interferences from Sr-90, but also from Y-90, potentially present in samples containing high levels of radioactivity. Experiments using a collision cell to eliminate isobaric interferences in a triple quadrupole mass spectrometer (ICP-QQQMS) have also been carried out, but results have demonstrated insufficient decontamination factors for nuclear forensic applications.