A Cl stable isotope fractionation factor between amphibole and fluid has been determined at 700 °C and 0.2 GPa. Rates of isotope exchange between pargasite and water at 600-800 °C were slow; therefore synthesis of amphibole in the presence of a fluid was necessary to facilitate the incorporation of Cl into amphibole. Hastingsite was synthesized from an oxide mixture and reacted with a NaCl-bearing supercritical fluid for periods of 3 to 14 days, approximately at the wüstite-magnetite buffer. Based on these synthesis-reaction experiments, the fractionation between hastingsite and a NaCl-bearing solution (~20000 ppm Cl) at 700 °C is 103lnαamphibole-fluid = 0.19‰ ± 0.23‰. These data display near zero fractionation at 700 °C, but suggest that amphibole is slightly enriched in 37Cl relative to the fluid, in agreement with empirical and theoretical results. / text

Calcium phosphates are important compounds as they exist in natural aqueous systems such as rivers, lakes, ocean, and soil. These calcium phosphates are widely used to provide information on paleotemperatures as well as many anthropological features, such as paleodiets. One of the most ubiquitous forms of calcium phosphate is hydroxyapatite (Ca10(PO4)6(OH)2) which is a major component of hard tissue such as bones, fossils, and tooth enamel. The oxygen isotope systematics in the hydroxyapatite associated with carbonate-water system will provide further information to allow for the reconstruction of terrestrial and marine environments. For example, Fricke et al. (1998) used oxygen isotope analysis of the carbonate components of hydroxyapatite in tooth enamel of mammals to investigate changes in terrestrial climate. Therefore, the purpose of this research study was to examine the oxygen isotope systematics in inorganic carbonate-bearing hydroxyapatite and water at low temperatures. This Master’s thesis followed and modified the methods described in Lécuyer et al. (2010) in an attempt to synthesize hydroxyapatite crystals and carbonate-bearing hydroxyapatite. The crystals synthesized were characterized in terms of several conditions (i.e., influence of mixing rate and maturations, pH, and concentrations of NaHCO3). Methods to produce hydroxyapatite were developed and analyzed using X-Ray diffraction analysis. The results demonstrated a strong dependence of pH in the hydroxyapatite solutions. Moreover, the effect of concentrations of NaHCO3 was deemed to be essential in order to obtain the desired amount of structural carbonates in the hydroxyapatite crystals. Furthermore, this research evaluated the temperature dependence of oxygen isotopic fractionation between HAP-bound carbonate and water at 10, 25, and 40 oC. Our study is the first to assess the two mixing-rates experiments with different maturations (7 and 14 days) on the oxygen isotope effects and fractionation behaviour between HAP-bound carbonate and water. Both maturation time and the effect of initial concentration of NaHCO3 were found to be the most important in determining the equilibrium conditions in our experiments. / Dissertation / Master of Science (MSc)

Sublimation experiments have been carried out to determine the effect of the mineral dust content of porous ices on the isotopic composition of the sublimate gas over medium (days to weeks) timescales. Whenever mineral dust of any kind was present, the D/H ratio of the sublimated gas was seen to decrease with time from the bulk ratio. Fractionations of up to 2.5 were observed for dust mixing ratios of 9 wt% and higher of JSC MARS-1 regolith simulant 1-10 mum crushed and sieved fraction. These favored the presence of the light isotope, H2O, in the gas phase. The more dust was added to the mixture, the more pronounced was this effect. Theoretical modeling of gas migration within the porous samples and adsorption on the excavated dust grains was undertaken to explain the results. Adsorption onto the dust grains is able to explain the low D/H ratios in the sublimate gas if adsorption favors retention of HDO over H2O. This leads to significant isotopic enrichment of HDO on the dust over time and depletion in the amount of HDO escaping the system as sublimate gas. This effect is significant for planetary bodies on which water moves mainly through the gas phase and a significant surface reservoir of dust may be found, such as on Comets and Mars. For each of these, inferences about the bulk water D/H ratio as inferred from gas phase measurements needs to be reassessed in light of the volatile cycling history of each body.PACS CODES:98.80.Ft Isotopes, abundances and evolution (astronomy)], 64.70.Hz Sublimation], 68.43.-h Adsorption at solid surfaces]

Volatiles (H2O, CO2, S, Cl) play a key role in magmatic processes at subduction zones. In this study, the dissolved volatile contents of olivine-hosted melt inclusions from cinder cones in the Lassen segment of the Cascade arc are used to investigate dehydration of subducted oceanic lithosphere, magma formation in the sub-arc mantle wedge, and mafic magma storage and evolution in the crust. Relatively young, hot oceanic lithosphere subducts beneath the Cascade arc. The hydrogen-isotope and trace-element compositions of melt inclusions, when integrated with thermo-petrologic modeling, demonstrate that fluids in Cascade magmas are sourced from hydrated peridotite in the deep slab interior and that the oceanic crustal part of the slab extensively dehydrates beneath the forearc. In contrast to their slab-derived H, the melt inclusions have B concentrations and isotope ratios that are similar to mid-ocean ridge basalt (MORB), requiring little to no slab contribution of B, which is also consistent with extensive dehydration of the downgoing plate before it reaches sub-arc depths. Correlations of volatile and trace element ratios in the melt inclusions (H2O/Ce, Cl/Nb, Sr/Nd) demonstrate that geochemical variability in the magmas is the result of variable amounts of addition of a hydrous subduction component to the mantle wedge. Radiogenic isotope ratios require that the subduction component has less radiogenic Sr and Pb and more radiogenic Nd than the Lassen sub-arc mantle and is therefore likely to be a partial melt of subducted Gorda MORB. These results provide evidence that chlorite-derived fluids from the deep slab interior flux-melt the oceanic crust, producing hydrous slab melts that migrate into the overlying mantle, where they react with peridotite to induce further melting. The basaltic magmas that erupted at Cinder Cone near Mt. Lassen trapped melt inclusions during olivine crystallization at ~7-15 km depth. The melt inclusion compositions require that two different mantle-derived magmas were involved in the eruption, and temporal changes show that arrival of the two batches correlates with two explosive phases of activity. Both magmas experienced rapid crustal contamination before erupting, illustrating the complexities of cinder cone eruptions. This dissertation includes previously published and unpublished co-authored material.

No description available.

One of the most promising mitigation strategies for greenhouse gas accumulation in the atmosphere is carbon capture and storage (CCS). Deep saline aquifers are seen as the most efficient carbon dioxide (CO2) storage sites, mainly because of their vast size and worldwide distribution. Injecting CO2 into brine filled media will cause a physical and chemical disequilibrium in the formation. This PhD thesis documents the investigation of some of the resulting effects which occur at the beginning of the injection, during the injection period and millions of years after injection. When CO2 is injected into a brine filled reservoir, large amounts of in situ brine will be displaced away from the injection well. This causes a pressure increase in the vicinity of the well which may compromise the injection process. The simulation of this pressure increase was performed with the black-oil simulator Eclipse10 (Schlumberger) while using a number of recent formulas to predict the mutual dissolution and the fluid properties of CO2 and brine. The results show that the pressure increase can exceed the maximum sustainable pore pressure and will cause fracturing of the reservoir formation. The pore pressure increase is dependent on parameters such as temperature and salinity because they change the fluid properties of the CO2 and brine, but also the capability of the fluids to dissolve mutually. The mutual dissolution has generally a pressure reducing effect although its impact is regarded to be overestimated. This is mainly because reservoir engineering software cannot simulate the shock front realistically. Undulations, which appear on the injection pressure profile are not a result of model instabilities but can either be related to enhanced mutual dissolution due to grid effects, or to the software which may overestimate or underestimate the pressure and dissolution. A detailed investigation of those undulations is vital for the interpretation of the injection pressure. High fluid pressure can be an important parameter for the estimation of the CO2 storage capacity of saline aquifers such as the offshore Bunter Sandstone Formation, in the UK southern North Sea. Based on fluid pressure, the 1 storage capacity was calculated using the ECLIPSE compositional simulation package and a simple analytical equation. The estimated storage capacity is 6.55 to 7.17 Gt of CO2 calculated with the analytical and the numerical approach respectively. By comparing the results, the differences are relatively moderate and therefore the application of the numerical simulator is not regarded as necessary. This is mainly due to the effective pressure flow which prevents pressure accumulations underneath the cap rock. Although the CO2 storage capacity of the Bunter Sandstone Formation remains high, a previous survey, which was not based on fluid pressure, calculated a storage capacity approximately twice as high as the results presented here. In theory, due to the increase in CO2 concentration, CO2 bearing carbonate minerals could precipitate when CO2 is injected into an aquifer such as the Rotliegend aquifer in the southern North Sea. Geochemical models often predict a relatively rapid growth of carbonate minerals as the most secure form of long term engineered CO2 storage. But validation of model-results remains difficult due to the long periods of time involved. Natural analogue studies can bridge the gap between experiments and real-world storage. The Fizzy field, a southern North Sea (UK) gas accumulation with a high natural CO2 content (c. 50%) provides an ideal opportunity to study the long term effect of CO2 related mineral reaction. However all such reservoirs contain ‘normal’ diagenetic dolomite, so that distinguishing sequestration related dolomite is a challenge. CO2 was stepwise extracted from dolomite from both the Fizzy field and the Orwell Rotliegend sandstone in order to reveal any zonation of the crystals which could be related to enhanced dolomite precipitation due to the high CO2 concentration. According to the method between 0 and 22 % of the dolomite in the Fizzy field precipitated due to the high CO2 concentration. Therefore, between 0 and 19 % of the CO2, which is related to the relatively recent high CO2 concentration, is ‘trapped’ in the ‘sequestration dolomite’. The wide range of this estimate is mainly related to rock heterogeneity.

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.

In this dissertation, I discuss the role of organic residue analysis in identifying economic activities and subsistence practices associated with the first uses of pottery in the Middle East, and present the results of my analyses of 280 potsherds recovered from 22 Neolithic and early Chalcolithic settlements dating between 7300 and 4300 cal BC. The adoption of pottery vessels in the early agricultural villages and pastoral encampments of the Middle East was not a uniform phenomenon, with this new technology not immediately of benefit, apparently, to all human groups. Results of my analyses have demonstrated that ‘conventional’ solvent extraction and alkaline hydrolysis techniques have limited utility in the recovery of diagnostic organic compounds from pottery from early ceramic horizons in the Middle East (Gregg et al. 2007), and that increased yields can be achieved through the use of a microwave-assisted liquid chromatography protocol (Gregg et al. 2009; Gregg and Slater in press). My research has established that there is greater diversity in the fractionation of stable carbon isotopes associated with the synthesis of fatty acids in domesticated animals than has previously been reported. In many instances, the ranges of modern isotopic values that have been used to categorize animal fats in archaeological potsherds in northern Europe cannot distinguish between the ∂13C ratios of ancient dairy residues and carcass fats of ruminant and non-ruminant species in central Europe or the Middle East (Gregg et al. 2009; Gregg and Slater in press). In light of these results, I evaluate the diagnostic potential and limitations of different methodological approaches in the recovery and characterization of organic residues, and propose a series of measures that will allow more confident categorization of the substances in early pottery vessels from the Middle East. I also make a number of recommendations for archaeologists considering the use of organic residue analysis, and suggest some practical ideas on how to develop the degree of confidence necessary to assess the methods used in acquisition of molecular and isotopic data, and ultimately, to evaluate the adequacy of the analytical criteria used to address specific archaeological research questions.

In this dissertation, I discuss the role of organic residue analysis in identifying economic activities and subsistence practices associated with the first uses of pottery in the Middle East, and present the results of my analyses of 280 potsherds recovered from 22 Neolithic and early Chalcolithic settlements dating between 7300 and 4300 cal BC. The adoption of pottery vessels in the early agricultural villages and pastoral encampments of the Middle East was not a uniform phenomenon, with this new technology not immediately of benefit, apparently, to all human groups. Results of my analyses have demonstrated that ‘conventional’ solvent extraction and alkaline hydrolysis techniques have limited utility in the recovery of diagnostic organic compounds from pottery from early ceramic horizons in the Middle East (Gregg et al. 2007), and that increased yields can be achieved through the use of a microwave-assisted liquid chromatography protocol (Gregg et al. 2009; Gregg and Slater in press). My research has established that there is greater diversity in the fractionation of stable carbon isotopes associated with the synthesis of fatty acids in domesticated animals than has previously been reported. In many instances, the ranges of modern isotopic values that have been used to categorize animal fats in archaeological potsherds in northern Europe cannot distinguish between the ∂13C ratios of ancient dairy residues and carcass fats of ruminant and non-ruminant species in central Europe or the Middle East (Gregg et al. 2009; Gregg and Slater in press). In light of these results, I evaluate the diagnostic potential and limitations of different methodological approaches in the recovery and characterization of organic residues, and propose a series of measures that will allow more confident categorization of the substances in early pottery vessels from the Middle East. I also make a number of recommendations for archaeologists considering the use of organic residue analysis, and suggest some practical ideas on how to develop the degree of confidence necessary to assess the methods used in acquisition of molecular and isotopic data, and ultimately, to evaluate the adequacy of the analytical criteria used to address specific archaeological research questions.

Two new analytical methodologies were developed for chlorine and bromine stable isotope analyses of inorganic samples by Continuous-Flow Isotope Ratio Mass Spectrometry (CF-IRMS) coupled with gas chromatography (GC). Inorganic chloride and bromide were precipitated as silver halides (AgCl and AgBr) and then converted to methyl halide (CH3Cl and CH3Br) gases and analyzed. These new techniques require small samples sizes (1.4 µmol of Cl- and 1 µmol of Br-). The internal precision using pure CH3Cl gas is better than ∓0.04 ‰ (∓STDV) while the external precision using seawater standard is better than ∓0.07 ‰ (∓STDV). The internal precision using pure CH3Br gas is better than ∓0.03 ‰ (∓STDV) and the external precision using seawater standard is better than ∓0.06 ‰ (∓STDV). Moreover, the sample analysis time is much shorter than previous techniques. The analyses times for chlorine and bromine stable isotopes are 16 minutes which are 3-5 times shorter than all previous techniques. Formation waters from three sedimentary settings (the Paleozoic sequences in southern Ontario and Michigan, the Williston Basin and the Siberian Platform) were analyzed for 37Cl and 81Br isotopes. The δ37Cl and δ81Br values of the formation waters from these basins are characterized by large variations (between -1.31 ‰ and +1.82 ‰ relative to SMOC and between -1.50 ‰ and +3.35 ‰ relative to SMOB, respectively). A positive trend between δ81Br and δ37Cl values was found in all basins, where an enrichment of δ81Br is coupled by an enrichment of δ37Cl. In the Paleozoic sequences in southern Ontario and Michigan, the δ37Cl and δ81Br signatures of formation water collected from northwest of the Algonquin Arch are distinct from those collected from southeast of the Arch. All of the brines from the northwest of the Algonquin Arch are characterized by depleted isotopic values in comparison with the isotopic values from the brines from southeast of the Arch. The δ81Br signatures of the two brines show total separation with no overlaps. The δ37Cl values show some overlap between the two groups. One of the scenarios that can be put forward is that the Arch forms a water divide, where sediments southeast of the Arch are dominated by Appalachian Basin formation waters, and the sediments located northwest of the Arch are dominated by the Michigan Basin formation waters. The δ81Br and δ37Cl signatures of the Williston Basin brines suggest the existence of several different brines that are isotopically distinct and located in different stratigraphic units, even though they are chemically similar. The relatively wide range of δ37Cl and δ81Br of the formation waters suggests that the ocean isotopic signatures were variable over geologic time. A seawater temporal curve for δ81Br and δ37Cl was proposed with a larger variation of δ81Br in comparison with δ37Cl. The isotopic variations of these two elements agree very well with 87Sr/86Sr seawater variation during the same period. In general, the use of chlorine and bromine stable isotopes can be very useful in assessing the origin and the evolutionary processes involved in evolving formation waters and also in distinguishing different brines (end members). Furthermore, they can be employed to investigate the hydrogeological dynamics of sedimentary basins.