abstract: Meteorites and their components can be used to unravel the history of the early Solar System. Carbonaceous chondrites are meteorites that originated from undifferentiated parent bodies that formed within a few million years of the beginning of the Solar System. These meteorites contain calcium-aluminum-rich inclusions (CAIs), which are the oldest dated solids in the Solar System at ~4.567 billion years old and thus preserve a record of the earliest stage of Solar System formation. The isotopic compositions of CAIs and bulk carbonaceous chondrites can be used to identify the sources of material inherited by the protoplanetary disk, assess the degree of mixing in the disk, and evaluate sample origins and potential genetic relationships between parent bodies. In particular, mass-independent Cr and Ti isotopic compositions have proven to be especially useful for these purposes. In this work, I first developed new methods for the chemical separation of Cr and Ti, improving the reliability of existing methods to ensure consistent yields and accurate isotopic measurements. I then measured the Cr and Ti isotopic compositions of CAIs from CV and CK chondrites to determine the extent of isotopic heterogeneity in the CAI-forming region and assess the role of CAIs in the preservation of planetary-scale isotopic anomalies. My results show that all measured CAIs originated from a common isotopic reservoir that incorporated material from at least three distinct nucleosynthetic sources and preserved limited isotopic heterogeneity. These results also suggest that planetary-scale isotopic anomalies cannot be attributed solely to the transport of CAIs from one part of the solar nebula to another. I finally measured the Cr and Ti isotopic compositions of bulk CM, CO, and ungrouped chondrites to evaluate the relationship between CM and CO chondrites, which have been suggested to originate from either distinct but related parent bodies or a common compositionally heterogeneous parent body. My results suggest that CM, CO, and related ungrouped chondrites originated from distinct parent bodies that formed from similar precursor materials in nearby formation regions. These results may have implications for asteroid samples returned by the OSIRIS-REx and Hayabusa2 missions. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2020

Several thousand coastal perennially ice-covered oligotrophic lakes and ponds have been identified on the Antarctic continent. To date, most hydrochemical studies on Antarctica’s ice-covered lakes have been undertaken in the McMurdo Dry Valleys (more than 20 lakes/ponds studied since 1957) because of their proximity to the McMurdo research station and the New Zealand station Scott Base. Yet, little attention has been given to coastal ice-covered lakes situated in Antarctica’s central Queen Maud Land region, and more specifically in the Untersee Oasis: a polar Oasis that encompasses two large perennially ice-covered lakes (Lake Untersee & Lake Obersee), and numerous small ice-covered morainic ponds. Consequently, this PhD research project aims to describe and understand the distribution, ice cover phenology, and contemporary hydrochemistry of perennially ice-covered lakes and ponds located in the Untersee Oasis and their effect on the activity of the benthic microbial ecosystem. Lake Untersee, the largest freshwater coastal lake in central Queen Maud Land, was the main focus of this study. Its energy and water mass balance was initially investigated to understand its current equilibrium and how this perennially well-sealed ice-covered lake may evolve under changing climate conditions. Results suggest that Lake Untersee’s mass balance was in equilibrium between the late 1990s and 2018, and the lake is mainly fed by subglacial meltwater (55-60%) and by subaqueous melting of glacier ice (40-45%). A recursive stable water isotope (δD-δ18O) evolution model for well-sealed perennial ice-covered lakes that takes into account the effect of changing chemistry in residual waters on δD-δ18O values was then developed and determined that Lake Untersee is in isotopic steady-state. Modeling results also showed that Untersee most likely did not receive additional inputs from surface streams during the last 300–500 years at the time of sampling, in November-December 2017. However, in mid-January 2019, Untersee experienced a glacial lake outburst flood (GLOF) that increased the water level by 2 m (contributing 1.75×107 m3 of water), modifying its water chemistry and inorganic carbon load. High-resolution grain size and carbon isotope analyses of the benthic microbial mats suggest that GLOFs occurred periodically over the Holocene and that those events sporadically increased the primary productivity of its benthic microbial ecosystem. Finally, ice-covered ponds in the Oasis were identified and sampled to compare their morphometric properties, hydrochemical properties, and microbial mat activity with Lake Untersee. It was discovered that the Untersee Oasis ponds offer the full spectrum of ice cover types (i.e., perennial well-sealed, perennial and moat forming, and seasonally ice-covered) and that their hydrochemical properties depend on ice cover type. Empirical pond data was used to determine how Lake Untersee and the ponds themselves will evolve as they transition under a warming climate from well-sealed to moat forming and from moat forming to seasonally ice-covered.

<p>  </p> <p>Reconstructing past glacier and ice-sheet extents is important to better understand how glacial systems have responded to past climate changes in hope of constraining predictions of their responses to ongoing anthropogenic climate warming. As such, the most recent period of climatic variations, from the Last Glacial Maximum (LGM, ca. 21 ka) through today, is of great interest as a prominent example of how ice has reacted to past climatic warming events. Surface exposure dating utilizing cosmogenic nuclides can directly constrain when past ice deglaciated in current and former glacial landscapes. Numerous studies have utilized long-lived cosmogenic radionuclides (i.e., 10Be, 26Al) in polar regions to reconstruct glacial systems. However, due to prevalent non-erosive cold-based ice, prior nuclides from pre-LGM can be preserved. </p> <p>The research described in this dissertation applies <em>in situ </em>cosmogenic 14C (<em>in situ</em> 14C), an emerging geochronometer, to polar glacial landscapes in Sweden and Antarctica to constrain the timing and rate of glacial ice retreat. <em>In situ </em>14C more closely reflects the post-LGM deglacial signal in polar regions because it is less likely to preserve prior nuclides (inheritance) under minimally erosive ice. Our cosmogenic 10Be–26Al–14C concentrations near the Riukojietna ice cap, the last remaining ice cap in Sweden, combined with a sedimentary record from a proximal proglacial lake, indicate the ice cap likely survived during a warm period in the Holocene, but was less extensive than today. The <em>in situ</em> 14C exposure data from nunataks in western Dronning Maud Land (DML), East Antarctica indicate significant coastal thickening (up to 850 m) not predicted by models to date. In addition, this work dates the timing of post-LGM ice surface lowering in two drainage basins in western DML. These results demonstrate the significant contribution of <em>in situ</em> 14C in polar regions.</p> <p>In addition to applications of <em>in situ</em> 14C in polar regions, this work also describes the development of a compositionally dependent <em>in situ</em> 14C production rate calculator. The ability to extract <em>in situ</em> 14C from samples which quartz cannot be separated (either quartz-poor or fine-grained) would allow new avenues of research. The computational framework will be a useful tool in efforts to broaden the utility of <em>in situ</em> 14C to quartz-poor and fine-grained rock types. </p>

No description available.

<p>Biodegradation of petroleum hydrocarbons by microorganisms is one of the most effective methods used to remediate environmental systems. However, much of what is known is based on the ability of (mostly bacterial) species to degrade hydrocarbons under enrichment conditions in a laboratory setting. In order to refine biodegradation as a remediation method, there is a critical need to understand the dynamics and mechanisms of microbial communities under <em>in situ </em>conditions. The goal of this dissertation was to provide insight and knowledge into the function of microbial communities in petroleum-contaminated environments using a combination of DNA, lipid and isotopic analyses. Microbial biomass, community structure, carbon sources were assessed at two study sites: (1) a former industrial facility contaminated by PAHs and (2) coastal salt marshes impacted by the <em>Deepwater Horizon</em> oil spill.</p> <p>Isotopic analyses of soils collected from the PAH-contaminated site revealed that microbial carbon sources were derived from vegetation and/or natural organic matter present in soils matter rather than PAHs. Similarly, microbial community structure remained consistent across samples and there were no observed shifts in phylotype diversity with increasing levels of PAHs. Bioaccessibility assays revealed that a large fraction of soil-borne PAHs at the site are not bioavailable to microorganisms; thus, highlighting the importance of environmental factors to <em>in situ</em> biodegradation.</p> <p>Biodegradation of <em>Deepwater Horizon </em>spilled oil was detected in salt marsh sediments such that petroleum-derived carbon was a primary carbon source for indigenous microbial communities in the months following the spill. Likewise, pyrosequencing of all three microbial domains showed an increase in the relative of abundance of taxonomic groups known to include hydrocarbon-degrading species, such as <em>Sphingomonadales</em>. These results suggest that Gulf of Mexico marsh sediments have considerable biodegradation potential and that natural attenuation may be feasible remediation strategy in this region.</p> / Doctor of Philosophy (PhD)

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.

Os modelos para a formação de plútons alcalinos da Província Alcalina do Sudeste Brasileiro ou Alinhamento Poços de Caldas-Cabo Frio associam a gênese destas rochas a grandes reativações ou a passagem de uma pluma mantélica, registrada pelo traço de um hot spot. O objetivo desta tese é, apresentar novos dados e interpretações para contribuir com a melhor elucidação e discussão destes modelos. Os estudos incluem mapeamento, petrografia, litogeoquímica, geoquímica isotópica de Sr, Nd e Pb e datação 40Ar/39Ar. As intrusões selecionadas correspondem ao Morro Redondo, Mendanha e Morro de São João, no Rio de Janeiro, localizados em posições distintas no alinhamento Poços de Caldas-Cabo Frio. A intrusão alcalina do Morro Redondo é composta majoritariamente de nefelina sienitos e sienitos com nefelina, com rara ocorrência de rochas máficas e é caracterizada por uma suíte alcalina sódica insaturada em sílica, de caráter metaluminosa a peralcalina. Esta intrusão foi datada em aproximadamente 74 Ma (idade-platô 40Ar/39Ar). A intrusão alcalina do Mendanha é composta por diversos tipos de rochas sieníticas, além de brechas e estruturas subvulcânicas, como rochas piroclásticas e diques e caracteriza-se por ser uma suíte alcalina sódica saturada em sílica, de caráter metaluminosa, diferente do que ocorre no Marapicu, este subsaturado em sílica. Esta intrusão apresentou duas idades-platô 40Ar/39Ar distintas de magmatismo: 64 Ma para as rochas do Mendanha e 54 Ma em dique de lamprófiro, registrando magmatismo policíclico. O Morro do Marapicu foi datado em aproximadamente 80 Ma. Já a intrusão alcalina do Morro de São João possui uma ampla variedade de litotipos saturados a subsaturados em sílica, tais como sienitos, álcali-sienitos e monzossienitos (alguns portadores de pseudoleucita), com variedades melanocráticas, tais como malignitos e fergustios. Estas rochas definem suas distintas suítes alcalinas subsaturadas em sílica: Uma de composição sódica e outra potássica. Há também uma suíte alcalina saturada em sílica, definida por gabros alcalinos e shonkinitos. A petrogênese destas intrusões corresponde ao modelo de cristalização fracionada, com assimilação de rochas encaixantes (AFC) como indicado pela alta variabilidade de razões isotópicas de estrôncio. No Morro de São João é sugerido o modelo de mistura magmática. Estas intrusões foram geradas a partir de magmas mantélicos enriquecidos, possivelmente associados à antiga zona de subducção relacionada ao orógeno Ribeira. Em razão das novas idades obtidas, o modelo de hot spot proposto fica prejudicado, visto que o Marapicu é de idade mais antiga das intrusões analisadas, o que era esperado para o Morro Redondo. Alguns modelos projetam plumas mantélicas com aproximadamente 1000 km de diâmetro, o que poderia explicar o Mendanha ser contemporâneo ao Morro de São João. As assinaturas isotópicas obtidas para as intrusões não se associam à assinatura isotópica de Trindade e, caso o modelo de plumas mantélicas seja o correto, a pluma que teria maior semelhança de assinatura isotópica é a pluma de Tristão da Cunha. / The models for formation of alkaline plutons of the Southeastern Brazil Alkaline Province or Poços de Caldas-Cabo Frio Magmatic Lineament, which genetic modeling associates crust reactivations or mantle plumes, with definition of a hot spot track. The objective of this work is to report new data and interpretations to contribute to a better understanding and discussion about the model of alkaline rock generation. The studies involved geological mapping, petrography, litogeochemistry, Sr-Nd-Pb isotopes and 40Ar/39Ar geochronology. The selected alkaline complexes are the Morro Redondo, Mendanha and Morro de São João, located at Rio de Janeiro State. These intrusions are well-distributed along the Poços de Caldas-Cabo Frio Magmatic Lineament. The Morro Redondo alkaline intrusion is composed mainly by nepheline syenites and nepheline-bearing syenites and mafic rocks are rare. It was defined as a sodic silica-undersaturated alkaline suite, with metaluminous to peralkaline characteristics. The intrusion was dated at 74 Ma (40Ar/39Ar plateau age). The Mendanha alkaline intrusion is compose by various types of syenitic rocks, breccias and subvulcanic structures, as pyroclastic rocks and dikes. It was defined by a sodic silica-saturated alkaline suite with metaluminous characterisics. The intrusion presented two distinct 40Ar/39Ar ages for the magmatism: 64 Ma for Mendanha rocks and 54 Ma to lamprophyre dike, which illustrates a polycyclic magmatism. The Morro do Marapicu 40Ar/39Ar age yielded 80 Ma. The Morro de São João alkaline intrusion has a large variety of silica-undersaturated to silica-saturated rocks, as syenites, alkali-syenites and monzosyenites (some pseudoleucite-bearing), with melanocratic varieties, as malignites and ferguites. These rocks defined distinct alkaline silica-undersaturated suggenting sodic and potassic types. There was found an alkaline silica-saturated suite, defined by alkaline gabbros and shonkinites. The petrogenesis of these intrusions corresponds to the fractional crystallization, with assimilation of host rocks, and the crustal contamination is indicated by high variability of Sr isotope ratios. For Morro de São João origin is suggested a K-Na bimodal magma. These intrusions were generated from enriched mantle-derived magmas, possible associated to ancient subduction zone of Ribeira orogen. In terms of the new 40Ar/39Ar data, the hot spot model is not plausible, because the Morro do Marapicu is older than the other studied intrusions. Some models projected mantle plumes with 1000 Km size, what may explain the reason for Mendanha and Morro de São João have the nearly the same age. The obtained isotopic signatures for these intrusions were not associated to Trindade signature and, if the mantle plumes model is correct, the plume that has the most similar signature is Tristão da Cunha.

Due to Earth’s efficient crustal recycling through plate tectonics, the remaining physical record of Earth’s first two billion years consists of mineral fragments and heavily metamorphosed rocks in isolated Archean cratons. Characterization of Earth’s earliest tectonic processes requires investigation of all available records; the mineral garnet has been largely overlooked. The major element chemistry and samarium-neodymium (Sm-Nd) isotope ratios preserved in fragmented detrital garnet and Archean metamorphic garnet record the timing and conditions of early tectonic events. This work presents detailed methodology for a new detrital garnet geochronometer unlocking age information from previously undateable detrital garnet surviving recycling in sediment, sedimentary rocks, and metasedimentary rocks. The new method’s utility is demonstrated by dating garnet from a Scottish sedimentary rock and nineteen individual garnet grains from a tributary to the French Broad River in the southern Appalachians. In the southern Appalachians, garnet and existing monazite ages overlap (though the mean garnet age is slightly younger) to record the most recent metamorphic event and both are younger than inherited zircon ages. Proof-of-concept testing demonstrating protocol development for blank-correction and routine analysis of samples smaller than 1 ng advances small Sm-Nd analysis. Additionally, this work applies existing Sm-Nd garnet geochronology methods to search for garnet older than 2.5 Ga and provide age constraints on the complicated metamorphic histories of two Archean cratons. A search for detrital garnet in a sample from the Jack Hills metasedimentary belt of Western Australia hosting the Earth’s oldest known terrestrial materials (ca. 4.3 Ga) failed to produce garnet. Instead, two samples collected ~4 km south of the Jack Hills belt in the Narryer Terrane were dated to confirm Narryer regional metamorphism at ca. 2.6 Ga. The Acasta gneiss of northern Canada, arguably Earth’s oldest known cohesive rock outcrop (ca. 4.0 Ga), produced one of the Earth’s oldest known garnet ages. Garnet ages of ca. 2.95 Ga constrain the timing of Archean metamorphism and the data also indicate potential for preservation of even older garnet. Finally, a compilation of published garnet ages in the literature is presented to summarize the community’s progress in the search for Earth’s oldest garnet. / 2017-12-06T00:00:00Z

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.