A number of leaks of radioactive liquors to ground are known to have occurred from several plant buildings, vaults and disposal trenches within and around the Separation area at the Sellafield nuclear site over the past 50 years1. The most significant of these leaks have occurred from the Magnox Silo, the Caesium Extraction Plant, the Magnox Reprocessing Pump House, the Sludge Storage Tanks, the Burial Pits and the Medium Active Evaporation and Thermal Denitration Plant. The radioactive contamination will be accompanied by other components of spent fuel reprocessing, including inorganic salts from neutralised acids, solvents and other organic compounds along with the typical contaminants commonly associated with large industrial activity such as heavy metals, fuel, oils, degreasing agents etc. The research in this thesis describes the effects of common industrial contaminants on the behaviour of Cs and Sr sorption to bentonite and montmorillonite clay minerals. Batch sorption experiments of Cs and Sr uptake onto bentonite and montmorillonite in a number of complex systems were investigated as follows: 1. Initial batch sorption experiments investigating the normal behaviour of the clay minerals. 2. Introduction of anthropogenic organic ligands EDTA, NTA and picolinic acid into the system and their influence on Sr and Cs uptake. 3. Time dependent studies investigating the effect that residence time of the anthropogenic organic ligands has on the sorption properties of montmorillonite and bentonite. 4. Quaternary systems where simulant Magnox sludge equilibrated water, at a number of concentrations, was introduced to ternary systems containing anthropogenic organic ligands. 5. Time dependent studies investigating the effect of hydrocarbons TCE, toluene and naphthalene on the uptake of Cs and Sr to bentonite and montmorillonite. The batch sorption experiments show that the presence of anthropogenic organic ligands reduces the uptake of Cs and Sr by both montmorillonite and bentonite. It is also shown that the presence of simulant Magnox sludge in quaternary systems can also reduce the uptake of Cs and Sr, with significant reductions in sorption observed for Sr sorption in EDTA quaternary systems. Further, the uptake of Cs and Sr to bentonite and montmorillonite appears to decrease with increasing anthropogenic organic ligand residence time. This suggests that the ligands are altering the surface of the clay minerals reducing the number of available binding sites. The influence of hydrocarbons shows a significant decrease in sorption after 3 months for Cs and Sr sorption to montmorillonite. There were no further significant changes for all other hydrocarbon systems investigated.

published_or_final_version / abstract / Orthopaedics and Traumatology / Doctoral / Doctor of Philosophy

published_or_final_version / Orthopaedics and Traumatology / Master / Master of Philosophy

The Laramide Rocky Mountains in western U.S.A is an important topographic feature in the continental interior, yet its formation and evolution are poorly constrained. This study uses the oxygen and strontium isotope geochemistry of freshwater bivalve fossils from six Laramide basins in order to reconstruct the spatial evolution of the paleotopography and Precambrian basement erosion in late Cretaceous-early Eocene. In addition it uses the sedimentology, detrital zircon U-Pb geochronology, and isotope paleoaltimetry of early Eocene sedimentary strata to constrain the tectonic setting, paleogeography and paleoclimate of the Wind River basin. Annual and seasonal variation in ancient riverwater δ¹⁸O reconstructed from shell fossils shows that the Canadian Rocky Mountains was 4.5±1.0 km high in late Cretaceous-early Paleocene, and the Laramide ranges in eastern Wyoming reached 4.5±1.3 km high, while the ranges in western Wyoming were 1-2 km high in late Paleocene. The ⁸⁷Sr/⁸⁶Sr ratios of riverwaters reconstructed from the same fossils show that Proterozoic metamorphic carbonates in the Belt-Purcell Supergroup were not exposed in the Canadian Rocky Mountains during Late Cretaceous-early Paleocene, but that Precambrian silicate basement rock was exposed and eroded in the Laramide ranges during late Paleocene-early Eocene. The sedimentary environment of the early Eocene Wind River basin changed from gravelly fluvial and/or stream-dominated alluvial fan to low-sinuosity fluvial systems. Tectonic uplift of the Washakie and Wind River Range in early Eocene formed the modern paleodrainage system, although the elevation of the basin floor was only ~500 m high at that time, and early Eocene paleoclimate is more humid than modern climate.

Applications of lead and strontium isotope analysis were made on archaeological materials from three different contexts in both the Old and New Worlds. These materials comprised pre-Hispanic glaze painted ceramics from Arizona, U.S.A., glass beads from late first millennium AD Igbo-Ukwu, Nigeria, and copper-based metals from early first millennium AD Kissi, Burkina Faso. All materials contain lead at major, minor, or trace concentrations, and lead isotope analysis was employed to determine a provenance for that lead. Strontium isotope analysis also was applied to glass beads from Igbo-Ukwu to determine provenance(s) for strontium found in the glass. Furthermore, application of elemental composition analysis was or had been employed on all samples for additional data comparisons within assemblages and with comparable archaeological materials.Results of these analyses determined, in most cases, regional provenance with high degrees of confidence for lead contained in the analyzed samples. Strontium and elemental composition analysis data also proved valuable in confirming the regional provenance of the raw glass used to produce the glass beads. Leads in the glaze paints from Arizona, which demonstrated a range of resources exploitation, were confidently restricted to a few regions for their procurement. Likewise leads in most glass beads from Igbo-Ukwu were confidently restricted to two main source regions, with a third strong contender also being identified. The elemental composition and strontium isotope data determined with confidence the production regions for the primary raw glasses used to make the glass beads. Finally, leads in copper-based metals from Burkina Faso also were restricted to a few regions, although some inconclusiveness in provenance determination was attributed to mixing of metals from difference sources.These results confirm the utility of heavy isotope analysis of archaeological materials for provenance determination. The combination of these data with elemental composition analyses further confirm the interpretive strength of combining independent but related sets of analytical data for exploring questions of archaeological provenance. With improvements in instrument technology and application in the past two decades, very high precision and high accuracy analyses can be made which eliminate some earlier concerns of heavy isotope applications in archaeology.

Lead and strontium isotopes are two powerful tracers that can be used to identify or constrain the provenance of a wide range of archaeological materials, but these two isotopic tracers have been rarely employed to infer the sources of artifacts in the southwestern USA. This dissertation contains four studies that demonstrate how these isotopic systems can address questions about the sources of three types of archaeological materials found in this region: turquoise, lead-based glaze-paints, and metals. The analysis of 116 samples of turquoise from 17 deposits in the southwestern USA reveals that lead and strontium isotopes are robust and sensitive tracers of turquoise at multiple scales. Isotopic variation among turquoise deposits correlates with broad regional differences in the geologic and tectonic setting of the rocks and mineral deposits which host turquoise mineralization. Many turquoise deposits also have unique isotopic signatures that will enable insights into ancient patterns of turquoise acquisition at regional and local levels. To show the utility of these tracers when applied to archaeological turquoise, I use lead and strontium isotopic measurements to establish that the Silver Bell Mountains are the likely source turquoise found at the Redtail site in the Tucson Basin, Arizona, USA. This dissertation also contains new, high-precision isotopic ratios of lead ores (galena and cerrusite) from four mining districts in New Mexico, including the Cerrillos Hills. All districts studied are possible sources of lead used by Pueblo IV communities to produce glaze paints. These new measurements, made by multiple-collector ICP-MS, define the isotopic composition of the ore deposits with greater precision and accuracy than achieved in previous studies, indicating an opportunity to improve interpretations about the provenance of lead in glaze paints. Lead isotopes are also found to be useful tools for identifying lead and copper metal associated with the 1540-1542 Vázquez de Coronado expedition. Lead shot and copper crossbow boltheads from two sites with archaeological evidence for the expedition's presence were determined to share similar or identical lead isotopic ratios. I propose this specific isotopic "fingerprint" can be used to identify other artifacts belonging to the expedition in the Southwest.

No description available.

No description available.

This thesis undertakes a complete reinvestigation of the archaeology of a large Early Bronze Age cemetery at İkiztepe in northern Turkey, by utilizing oxygen and strontium isotope analysis of human remains in combination with spatial and biodistance analysis and various dating techniques to identify potential immigrants to the site and to examine larger issues of residential mobility and social organization. The occupation of the Northern Anatolian site of İkiztepe is traditionally assigned to the Late Chalcolithic and Early Bronze Ages. However, the site’s chronological framework has been challenged in recent years. These chronological issues have been addressed by applying fluoride and AMS radiocarbon dating to the skeletal remains from the İkiztepe cemetery, to develop an absolute and relative chronology for the burials. These results have shown that the cemetery dates at least a millennium earlier than previously supposed. Oxygen and strontium isotope analyses allowed the identification of individuals whose bone chemistry suggests that they were possible long distance immigrants to the site of İkiztepe, as well as suggesting the existence of a group of mobile individuals who may represent a transhumant segment of the İkiztepe population. Spatial and biodistance analyses suggest that principles of cemetery organization in this period were highly complex. Immigrant individuals and nomadic or semi-nomadic segments of the population do not appear to have been distinguished in any observable way from their sedentary local counterparts, displaying similar burial types, grave goods and spatial locations. Furthermore, burial within the İkiztepe cemetery does not appear to have been kin structured. These results suggest that assumptions about funerary practices as important indicators of cultural identity and lineage affiliation may represent an over-simplification of complex patterns of interaction and integration among and within populations and cultural groups.

No description available.