Matching Items (26)
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Description
Carbonaceous chondrites (CCs) present a unique opportunity for learning about the earliest organic chemistry that took place in our Solar System. The complex and diverse suite of meteoritic organic material is the result of multiple settings and physicochemical processes, including aqueous and thermal alteration. Though meteorites often inform origin-of-life discussions

Carbonaceous chondrites (CCs) present a unique opportunity for learning about the earliest organic chemistry that took place in our Solar System. The complex and diverse suite of meteoritic organic material is the result of multiple settings and physicochemical processes, including aqueous and thermal alteration. Though meteorites often inform origin-of-life discussions because they could have seeded early Earth with significant amounts of water and pre-biotic, organic material, their record of abiotic, aqueous, and organic geochemistry is of interest as well.

CC materials previously resided on asteroidal parent bodies, relic planetesimals of Solar System formation which never accreted enough material to develop long-lived, large-scale geological processes. These bodies were large enough, however, to experience some degree of heating due to the decay of radiogenic isotopes, and the meteorite record suggests the existence of 100-150 parent bodies which experienced varying degrees of thermal and aqueous alteration for the first several 10 Myr of Solar System history.

The first chapter of this dissertation reviews literature addressing aqueous alteration as an essential participant in parent body geochemistry, organic synthesis, or both (though papers which address both are rare). The second chapter is a published organic analysis of the soluble organic material of Bells, an unclassified type 2 chondrite. Analytical approaches to assess terrestrial contamination of meteorite samples are also reviewed in the first chapter to allow introduction in chapter 3 of kinetic modeling which rules out certain cases of contamination and constrains the timing of thermal and aqueous alteration. This is the first known application of isoleucine epimerization for either of these purposes. Chapter 4 is a kinetic study of D-allo-isoleucine epimerization to establish its behavior in systems with large, relative abundances of alloisoleucine to isoleucine. Previous epimerization studies for paleontological or geological purposes began with L-isoleucine, the only protein amino acid of the four isoleucine stereoisomers.

Kinetic model calculations using isoleucine stereoisomer abundances from 7 CR chondrites constrain the total duration of the amino acids' residence in the aqueous phase. The comparatively short timescales produced by the presented modeling elicit hypotheses for protection or transport of the amino acids within the CR parent body.
ContributorsMonroe, Adam Alexander (Author) / Pizzarello, Sandra (Thesis advisor) / Williams, Peter (Thesis advisor) / Anbar, Ariel D (Committee member) / Shock, Everett L (Committee member) / Arizona State University (Publisher)
Created2014
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Description
The hydrothermal chemistry of organic compounds influences many critical geological processes, including the formation of oil and gas reservoirs, the degradation and transport of organic matter in sedimentary basins, metabolic cycles in the deep subsurface biosphere, and possibly prebiotic organic synthesis related to the origin of life. In most

The hydrothermal chemistry of organic compounds influences many critical geological processes, including the formation of oil and gas reservoirs, the degradation and transport of organic matter in sedimentary basins, metabolic cycles in the deep subsurface biosphere, and possibly prebiotic organic synthesis related to the origin of life. In most previous studies of hydrothermal organic reactions the emphasis has been mainly on determining reaction product distributions, studies that provide detailed mechanistic information or direct evidence for specific reaction intermediates are rare. To develop a better understanding, I performed hydrothermal experiments with model ketone compound dibenzylketone (DBK), which serves as a quite useful tool to probe the bond breaking and forming processes in hydrothermal geochemical transformations. A careful study of reaction kinetics and products of DBK in Chapter 2 of this dissertation reveals reversible and irreversible reaction pathways, and provides evidence for competing ionic and radical reaction mechanisms. The majority of the observed products result from homolytic carbon-carbon and carbon-hydrogen bond cleavage and secondary coupling reactions of the benzyl and related radical intermediates.

In the third chapter of the dissertation, a novel hydrothermal photochemical method is studied, which enabled in situ independent generation of the relevant radicals and effectively separated the radical and ionic reactions that occur simultaneously in pure thermal reactions. In the following chapter, I focus on the role of minerals on ketone hydrothermal reactions. Minerals such as quartz and corundum have no detectable effect on DBK, whereas magnetite, hematite, and troilite all increase ketone reactivity to various extents. The influence of these iron-bearing minerals can be attributed to the mineral surface catalysis or the solution chemistry change that is presumably caused by dissolved inorganic species from minerals. In addition, some new discoveries on strong oxidizing effect of copper (II) ion under hydrothermal conditions are described in the latter chapter of the dissertation, where examples of clean and rapid reactions that converted alcohols to aldehyde and aldehydes to carboxylic acids are included.
ContributorsYang, Ziming (Author) / Shock, Everett L (Thesis advisor) / Gould, Ian R (Committee member) / Wolf, George H. (Committee member) / Arizona State University (Publisher)
Created2014
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Description
The occurrence of exogenic, meteoritic materials on the surface of any world presents opportunities to explore a variety of significant problems in the planetary sciences. In the case of Mars, meteorites found on its surface may help to 1) constrain atmospheric conditions during their time of arrival; 2) provide insights

The occurrence of exogenic, meteoritic materials on the surface of any world presents opportunities to explore a variety of significant problems in the planetary sciences. In the case of Mars, meteorites found on its surface may help to 1) constrain atmospheric conditions during their time of arrival; 2) provide insights into possible variabilities in meteoroid type sampling between Mars and Earth space environments; 3) aid in our understanding of soil, dust, and sedimentary rock chemistry; 4) assist with the calibration of crater-age dating techniques; and 5) provide witness samples for chemical and mechanical weathering processes. The presence of reduced metallic iron in approximately 88 percent of meteorite falls renders the majority of meteorites particularly sensitive to oxidation by H2O interaction. This makes them excellent markers for H2O occurrence. Several large meteorites have been discovered at Gusev Crater and Meridiani Planum by the Mars Exploration Rovers (MERs). Significant morphologic characteristics interpretable as weathering features in the Meridiani suite of iron meteorites include a 1) large pit lined with delicate iron protrusions suggestive of inclusion removal by corrosive interaction; 2) differentially eroded kamacite and taenite lamellae on three of the meteorites, providing relative timing through cross-cutting relationships with deposition of 3) an iron oxide-rich dark coating; and 4) regmaglypted surfaces testifying to regions of minimal surface modification; with other regions in the same meteorites exhibiting 5) large-scale, cavernous weathering. Iron meteorites found by Mini-TES at both Meridiani Planum and Gusev Crater have prompted laboratory experiments designed to explore elements of reflectivity, dust cover, and potential oxide coatings on their surfaces in the thermal infrared using analog samples. Results show that dust thickness on an iron substrate need be only one tenth as great as that on a silicate rock to obscure its infrared signal. In addition, a database of thermal emission spectra for 46 meteorites was prepared to aid in the on-going detection and interpretation of these valuable rocks on Mars using Mini-TES instruments on both MER spacecraft. Applications to the asteroidal sciences are also relevant and intended for this database.
ContributorsAshley, James Warren (Author) / Christensen, Philip R. (Thesis advisor) / Sharp, Thomas G (Committee member) / Shock, Everett L (Committee member) / Hervig, Richard L (Committee member) / Zolotov, Mikhail Y (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Molybdenum (Mo) is a key trace nutrient for biological assimilation of nitrogen, either as nitrogen gas (N2) or nitrate (NO3-). Although Mo is the most abundant metal in seawater (105 nM), its concentration is low (<5 nM) in most freshwaters today, and it was scarce in the ocean before 600

Molybdenum (Mo) is a key trace nutrient for biological assimilation of nitrogen, either as nitrogen gas (N2) or nitrate (NO3-). Although Mo is the most abundant metal in seawater (105 nM), its concentration is low (<5 nM) in most freshwaters today, and it was scarce in the ocean before 600 million years ago. The use of Mo for nitrogen assimilation can be understood in terms of the changing Mo availability through time; for instance, the higher Mo content of eukaryotic vs. prokaryotic nitrate reductase may have stalled proliferation of eukaryotes in low-Mo Proterozoic oceans. Field and laboratory experiments were performed to study Mo requirements for NO3- assimilation and N2 fixation, respectively. Molybdenum-nitrate addition experiments at Castle Lake, California revealed interannual and depth variability in plankton community response, perhaps resulting from differences in species composition and/or ammonium availability. Furthermore, lake sediments were elevated in Mo compared to soils and bedrock in the watershed. Box modeling suggested that the largest source of Mo to the lake was particulate matter from the watershed. Month-long laboratory experiments with heterocystous cyanobacteria (HC) showed that <1 nM Mo led to low N2 fixation rates, while 10 nM Mo was sufficient for optimal rates. At 1500 nM Mo, freshwater HC hyperaccumulated Mo intercellularly, whereas coastal HC did not. These differences in storage capacity were likely due to the presence in freshwater HC of the small molybdate-binding protein, Mop, and its absence in coastal and marine cyanobacterial species. Expression of the mop gene was regulated by Mo availability in the freshwater HC species Nostoc sp. PCC 7120. Under low Mo (<1 nM) conditions, mop gene expression was up-regulated compared to higher Mo (150 and 3000 nM) treatments, but the subunit composition of the Mop protein changed, suggesting that Mop does not bind Mo in the same manner at <1 nM Mo that it can at higher Mo concentrations. These findings support a role for Mop as a Mo storage protein in HC and suggest that freshwater HC control Mo cellular homeostasis at the post-translational level. Mop's widespread distribution in prokaryotes lends support to the theory that it may be an ancient protein inherited from low-Mo Precambrian oceans.
ContributorsGlass, Jennifer (Author) / Anbar, Ariel D (Thesis advisor) / Shock, Everett L (Committee member) / Jones, Anne K (Committee member) / Hartnett, Hilairy E (Committee member) / Elser, James J (Committee member) / Fromme, Petra (Committee member) / Arizona State University (Publisher)
Created2011
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Description
The San Andreas Fault (SAF) is the primary structure within a system of faults accommodating motion between the North American and Pacific plates. Physical models of faulting and characterizations of seismic hazard are informed by investigations of paleoseismology, slip distribution, and slip rate. The impact of earthquakes on people is

The San Andreas Fault (SAF) is the primary structure within a system of faults accommodating motion between the North American and Pacific plates. Physical models of faulting and characterizations of seismic hazard are informed by investigations of paleoseismology, slip distribution, and slip rate. The impact of earthquakes on people is due in large part to social vulnerability. This dissertation contributes an analysis about the relationships between earthquake hazard and social vulnerability in Los Angeles, CA and investigations of paleoseismology and fault scarp array complexity on the central SAF. Analysis of fault scarp array geometry and morphology using 0.5 m digital elevation models along 122 km of the central SAF reveals significant variation in the complexity of SAF structure. Scarp trace complexity is measured by scarp separation, changes in strike, fault trace gaps, and scarp length per SAF kilometer. Geometrical complexity in fault scarp arrays indicates that the central SAF can be grouped into seven segments. Segment boundaries are controlled by interactions with subsidiary faults. Investigation of an offset channel at Parkfield, CA yields a late Holocene slip rate of 26.2 +6.4/- 4.3 mm/yr. This rate is lower than geologic measurements on the Carrizo section of the SAF and rates implied by far-field geodesy. However, it is consistent with historical observations of slip at Parkfield. Paleoseismology at Parkfield indicates that large earthquakes are absent from the stratigraphic record for at least a millennia. Together these observations imply that the amount of plate boundary slip accommodated by the main SAF varies along strike. Contrary to most environmental justice analyses showing that vulnerable populations are spatially-tied to environmental hazards, geospatial analyses relating social vulnerability and earthquake hazard in southern California show that these groups are not disproportionately exposed to the areas of greatest hazard. Instead, park and green space is linked to earthquake hazard through fault zone regulation. In Los Angeles, a parks poor city, the distribution of social vulnerability is strongly tied to a lack of park space. Thus, people with access to financial and political resources strive to live in neighborhoods with parks, even in the face of forewarned risk.
ContributorsToké, Nathan A (Author) / Arrowsmith, J R (Thesis advisor) / Boone, Christopher G (Committee member) / Heimsath, Arjun M (Committee member) / Shock, Everett L (Committee member) / Whipple, Kelin X (Committee member) / Arizona State University (Publisher)
Created2011
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Description
This dissertation examines two topics of emerging interest in the field of organic geochemistry. The topic of the first portion of the dissertation is cold organic geochemistry on Saturn's moon Titan. Titan has an atmosphere and surface that are rich in organic compounds. Liquid hydrocarbons exist on the surface, most

This dissertation examines two topics of emerging interest in the field of organic geochemistry. The topic of the first portion of the dissertation is cold organic geochemistry on Saturn's moon Titan. Titan has an atmosphere and surface that are rich in organic compounds. Liquid hydrocarbons exist on the surface, most famously as lakes. Photochemical reactions produce solid organics in Titan's atmosphere, and these materials settle onto the surface. At the surface, liquids can interact with solids, and geochemical processes can occur. To better understand these processes, I developed a thermodynamic model that can be used to calculate the solubilities of gases and solids in liquid hydrocarbons at cryogenic temperatures. The model was parameterized using experimental data, and provides a good fit to the data. Application of the model to Titan reveals that the equilibrium composition of surface liquids depends on the abundance of methane in the local atmosphere. The model also indicates that solid acetylene should be quite soluble in surface liquids, which implies that acetylene-rich rocks should be susceptible to chemical erosion, and acetylene evaporites may form on Titan. In the latter half of this dissertation, I focus on hot organic geochemistry below the surface of the Earth. Organic compounds are common in sediments. Burial of sediments leads to changes in physical and chemical conditions, promoting organic reactions. An important organic reaction in subsurface environments is decarboxylation, which generates hydrocarbons and carbon dioxide from simple organic acids. Fundamental knowledge about decarboxylation is required to better understand how the organic and inorganic compositions of sediments evolve in response to changing geochemical conditions. I performed experiments with the model compound phenylacetic acid to obtain information about mechanisms of decarboxylation in hydrothermal fluids. Patterns in rates of decarboxylation of substituted phenylacetic acids point to a mechanism that proceeds through a ring-protonated zwitterion of phenylacetic acid. In contrast, substituted sodium phenylacetates exhibit a different kinetic pattern, one that is consistent with the formation of the benzyl anion as an intermediate. Results from experiments with added hydrochloric acid or sodium hydroxide, and deuterated water agree with these interpretations. Thus, speciation dictates mechanism of decarboxylation.
ContributorsGlein, Christopher R (Author) / Shock, Everett L (Thesis advisor) / Hartnett, Hilairy E (Committee member) / Zolotov, Mikhail Y (Committee member) / Williams, Lynda B (Committee member) / Gould, Ian R (Committee member) / Arizona State University (Publisher)
Created2012
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Description
In many natural systems aqueous geochemical conditions dictate the reaction pathways of organic compounds. Geologic settings that span wide ranges in temperature, pressure, and composition vastly alter relative reaction rates and resulting organic abundances. The dependence of organic reactions on these variables contributes to planetary-scale nutrient cycling, and suggests that

In many natural systems aqueous geochemical conditions dictate the reaction pathways of organic compounds. Geologic settings that span wide ranges in temperature, pressure, and composition vastly alter relative reaction rates and resulting organic abundances. The dependence of organic reactions on these variables contributes to planetary-scale nutrient cycling, and suggests that relative abundances of organic compounds can reveal information about inaccessible geologic environments, whether from the terrestrial subsurface, remote planetary settings, or even the distant past (if organic abundances are well preserved). Despite their relevance to planetary modeling and exploration, organic reactions remain poorly characterized under geochemically relevant conditions, especially in terms of their reaction kinetics, mechanisms, and equilibria.

In order to better understand organic transformations in natural systems, the reactivities of oxygen- and nitrogen-bearing organic functional groups were investigated under experimental hydrothermal conditions, at 250°C and 40 bar. The model compounds benzylamine and α-methylbenzylamine were used as analogs to environmentally relevant amines, ultimately elucidating two dominant deamination mechanisms for benzylamine, SN1 and SN2, and a single SN1 mechanism for deamination of α-methylbenzylamine. The presence of unimolecular and bimolecular mechanisms has implications for temperature dependent kinetics, indicating that Arrhenius rate extrapolation is currently unreliable for deamination.

Hydrothermal experiments with benzyl alcohol, benzylamine, dibenzylamine, or tribenzylamine as the starting material indicate that substitution reactions between these compounds (and others) are reversible and approach metastable equilibrium after 72 hours. These findings suggest that relative ratios of organic compounds capable of substitution reactions could be targeted as tracers of inaccessible geochemical conditions.

Metastable equilibria for organic reactions were investigated in a natural low-temperature serpentinizing continental system. Serpentinization is a water-rock reaction which generates hyperalkaline, reducing conditions. Thermodynamic calculations were performed for reactions between dissolved inorganic carbon and hydrogen to produce methane, formate, and acetate. Quantifying conditions that satisfy equilibrium for these reactions allows subsurface conditions to be predicted. These calculations also lead to hypotheses regarding active microbial processes during serpentinization.
ContributorsRobinson, Kirtland J (Author) / Shock, Everett L (Thesis advisor) / Herckes, Pierre (Committee member) / Hartnett, Hilairy E (Committee member) / Anbar, Ariel D (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Explosive mafic (basaltic) volcanism is not easily explained by current eruption models, which predict low energy eruptions from low viscosity magma due to decoupling of volatiles (gases). Sunset Crater volcano provides an example of an alkali basalt magma that produced a highly explosive sub-Plinian eruption. I investigate the possible role

Explosive mafic (basaltic) volcanism is not easily explained by current eruption models, which predict low energy eruptions from low viscosity magma due to decoupling of volatiles (gases). Sunset Crater volcano provides an example of an alkali basalt magma that produced a highly explosive sub-Plinian eruption. I investigate the possible role of magmatic volatiles in the Sunset Crater eruption through study of natural samples of trapped volatiles (melt inclusions) and experiments on mixed-volatile (H2O-CO2) solubility in alkali-rich mafic magmas.

I conducted volatile-saturated experiments in six mafic magma compositions at pressures between 400 MPa and 600 MPa to investigate the influence of alkali elements (sodium and potassium) on volatile solubility. The experiments show that existing volatile solubility models do not accurately describe CO2 solubility at mid-crustal depths. I calculate thermodynamic fits for solubility in each composition and calibrate a general thermodynamic model for application to other mafic magmas. The model shows that the relative percent abundances of sodium, calcium, and potassium have the greatest influence on CO2 solubility in mafic magmas.

I analyzed olivine-hosted melt inclusions (MIs) from Sunset Crater to investigate pre-eruptive volatiles. I compared the early fissure activity to the sub-Plinian eruptive phases. The MIs are similar in major element and volatile composition suggesting a relatively homogeneous magma. The H2O content is relatively low (~1.2 wt%), whereas the dissolved CO2 content is high (~2300 ppm). I explored rehomogenization and Raman spectroscopy to quantify CO2 abundance in MI vapor bubbles. Calculations of post-entrapment bubble growth suggest that some MI bubbles contain excess CO2. This implies that the magma was volatile-saturated and MIs trapped exsolved vapor during their formation. The total volatile contents of MIs, including bubble contents but excluding excess vapor, indicate pre-eruptive magma storage from 10 km to 18 km depth.

The high CO2 abundance found in Sunset Crater MIs allowed the magma to reach volatile-saturation at mid-crustal depths and generate overpressure, driving rapid ascent to produce the explosive eruption. The similarities in MIs and volatiles between the fissure eruption and the sub-Plinian phases indicate that shallow-level processes also likely influenced the final eruptive behavior.
ContributorsAllison, Chelsea Maria (Author) / Clarke, Amanda B (Thesis advisor) / Hervig, Richard L (Committee member) / Roggensack, Kurt (Committee member) / Semken, Steven (Committee member) / Till, Christy B. (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Organic reactions in natural hydrothermal settings have relevance toward the deep carbon cycle, petroleum formation, the ecology of deep microbial communities, and potentially the origin of life. Many reaction pathways involving organic compounds under geochemically relevant hydrothermal conditions have now been characterized, but their mechanisms, in particular those involving

Organic reactions in natural hydrothermal settings have relevance toward the deep carbon cycle, petroleum formation, the ecology of deep microbial communities, and potentially the origin of life. Many reaction pathways involving organic compounds under geochemically relevant hydrothermal conditions have now been characterized, but their mechanisms, in particular those involving mineral surface catalysis, are largely unknown. The overall goal of this work is to describe these mechanisms so that predictive models of reactivity can be developed and so that applications of these reactions beyond geochemistry can be explored. The focus of this dissertation is the mechanisms of hydrothermal dehydration and catalytic hydrogenation reactions. Kinetic and structure/activity relationships show that elimination occurs mainly by the E1 mechanism for simple alcohols via homogeneous catalysis. Stereochemical probes show that hydrogenation on nickel occurs on the metal surface. By combining dehydration with and catalytic reduction, effective deoxygenation of organic structures with various functional groups such as alkenes, polyols, ketones, and carboxylic acids can be accomplished under hydrothermal conditions, using either nickel or copper-zinc alloy. These geomimetic reactions can potentially be used in biomass reduction to generate useful fuels and other high value chemicals. Through the use of earth-abundant metal catalysts, and water as the solvent, the reactions presented in this dissertation are a green alternative to current biomass deoxygenation/reduction methods, which often use exotic, rare-metal catalysts, and organic solvents.
ContributorsBockisch, Christiana (Author) / Gould, Ian R (Thesis advisor) / Hartnett, Hilairy E (Committee member) / Shock, Everett L (Committee member) / Arizona State University (Publisher)
Created2018
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Description
An exhaustive parameter study involving 133 dynamic crystallization experiments was conducted, to investigate the validity of the planetary embryo bow shock model by testing whether the cooling rates predicted by this model are consistent with the most dominant chondrule texture, porphyritic. Results show that using coarse-grained precursors and heating durations

An exhaustive parameter study involving 133 dynamic crystallization experiments was conducted, to investigate the validity of the planetary embryo bow shock model by testing whether the cooling rates predicted by this model are consistent with the most dominant chondrule texture, porphyritic. Results show that using coarse-grained precursors and heating durations ≤ 5 minutes at peak temperature, porphyritic textures can be reproduced at cooling rates ≤ 600 K/hr, rates consistent with planetary embryo bow shocks. Porphyritic textures were found to be commonly associated with skeletal growth, which compares favorably to features in natural chondrules from Queen Alexandra Range 97008 analyzed, which show similar skeletal features. It is concluded that the experimentally reproduced porphyritic textures are consistent with those of natural chondrules. This work shows heating duration is a major determinant of chondrule texture and the work further constrains this parameter by measuring the rate of chemical dissolution of relict grains. The results provide a robust, independent constraint that porphyritic chondrules were heated at their peak temperatures for ≤ 10 minutes. This is also consistent with heating by bow shocks. The planetary embryo bow shock model therefore remains a viable chondrule mechanism for the formation of the vast majority of chondrules, and the results presented here therefore strongly suggest that large planetary embryos were present and on eccentric orbits during the first few million years of the Solar System’s history.
ContributorsPerez, Alexandra Marie (Author) / Desch, Steven J (Thesis advisor) / Till, Christy B. (Committee member) / Schrader, Devin L (Committee member) / Arizona State University (Publisher)
Created2018