With the development and successful landing of the NASA Perseverance rover, there has been growing interest in identifying how evidence of ancient life may be preserved and recognized in the geologic record. Environments that enable fossilization of biological remains are termed, “taphonomic windows”, wherein signatures of past life may be detected. In this dissertation, I have sought to identify taphonomic windows in planetary-analog environments with an eye towards the exploration of Mars. In the first chapter, I describe how evidence of past microbial life may be preserved within serpentinizing systems. Owing to energetic rock-water reactions, these systems are known to host lithotrophic and organotrophic microbial communities. By investigating drill cores from the Samail Ophiolite in Oman, I report morphological and associated chemical biosignatures preserved in these systems as a result of subsurface carbonation. As serpentinites are known to occur on Mars and potentially other planetary bodies, these deposits potentially represent high-priority targets in the exploration for past microbial life. Next, I investigated samples from Atacama Desert, Chile, to understand how evidence of life may be preserved in ancient sediments formed originally in evaporative playa lakes. Here, I describe organic geochemical and morphological evidence of life preserved within sulfate-dominated evaporite rocks from the Jurassic-Cretaceous Tonel Formation and Oligocene San Pedro Formation. Because evaporative lakes are considered to have been potentially widespread on Mars, these deposits may represent additional key targets to search for evidence of past life. In the final chapter, I describe the fossilization potential of surficial carbonates by investigating Crystal Geyser, an active cold spring environment. Here, carbonate minerals precipitate rapidly in the presence of photosynthetic microbial mat communities. I describe how potential biosignatures are initially captured by mineralization, including cell-like structures and microdigitate stromatolites. However, these morphological signatures quickly degrade owing to diagenetic dissolution and recrystallization reactions, as well as textural coarsening that homogenizes the carbonate fabric. Overall, my dissertation underscores the complexity of microbial fossilization and highlights chemically-precipitating environments that may serve as high-priority targets for astrobiological exploration.

Mantle derived basalts along the entirety of the Earth’s Mid-Ocean Ridge (MOR) spreading centers are continuously altered by seawater, allowing the hydrosphere to subsume energy and exchange mass with the deep, slowly cooling Earth. Compositional heterogeneities inherent to these basalts—the result of innumerable geophysical and geochemical processes in the mantel and crust—generate spatial variation in the equilibrium states toward which these water-rock environments cascade. This alteration results in a unique distribution of precipitate assemblages, hydrothermal fluid chemistries, and energetic landscapes among ecosystems rooted within and above the seafloor. The equilibrium states for the full range of basalt compositional heterogeneity present today are calculated over all appropriate temperatures and extents of reaction with seawater, along with the non-equilibrium mixtures generated when hydrothermal fluids mix back into seawater. These mixes support ancient and diverse ecosystems fed not by the energy of the sun, but by the geochemical energy of the Earth. Facilitated by novel, high throughout code, this effort has yielded a high-resolution compositional database that is mapped back onto all ridge systems. By resolving the chemical and energetic consequences of basalt-seawater interaction to sub-ridge scales, alteration features that are globally homogeneous can be distinguished from those that are locally unique, guiding future field observations with testable geochemical and biochemical predictions.

The hydrous alteration of ultramafic rocks, known as serpentinization, produces some of the most reduced (H2 >1 mmolal) and alkaline (pH >11) fluids on Earth. Serpentinization can proceed even at the low-temperature conditions (<50°C) characteristic of most of Earth’s continental aquifers, raising questions on the limits of life deep in the subsurface and the magnitude in the flux of reduced volatiles to the surface. In this work, I explored the compositions and consequences of fluids and volatiles found in three low-temperature serpentinizing environments: (1) active hyperalkaline springs in ophiolites, (2) modern shallow and deep peridotite aquifers, and (3) komatiitic aquifers during the Archean.

Around 140 fluids were sampled from the Oman ophiolite and analyzed for their compositions. Fluid compositions can be accounted for by thermodynamic simulations of reactions accompanying incipient to advanced stages of serpentinization, as well as by simulations of mass transport processes such as fluid mixing and mineral leaching. Thermodynamic calculations were also used to predict compositions of end-member fluids representative of the shallow and deep peridotite aquifers that were ultimately used to quantify energy available to various subsurface chemolithotrophs. Calculations showed that sufficient energy and power supply can be available to support deep-seated methanogens. An additional and a more diverse energy supply can be available when surfacing deep-seated fluids mix with shallow groundwater in discharge zones of the subsurface fluid pathway. Finally, the consequence of the evolving continental composition during the Archean for the global supply of H2 generated through komatiite serpentinization was quantified. Results show that the flux of serpentinization-generated H2 could have been a significant sink for O2 during most of the Archean. This O2 sink diminished greatly towards the end of the Archean as komatiites became less common and helped set the stage for the Great Oxidation Event. Overall, this study provides a framework for exploring the origins of fluid and volatile compositions, including their redox state, that can result from various low-temperature serpentinizing environments in the present and past Earth and in other rocky bodies in the solar system.

My dissertation research broadly focuses on the geochemical and physical exchange of materials between the Earth’s crust and mantle at convergent margins, and how this drives the compositional diversity observed on the Earth’s surface. I combine traditional petrologic and geochemical studies of natural and experimental high-pressure mafic rocks, with thermodynamic modeling of high-pressure aqueous fluids and mafic-ultramafic lithologies allowing for more complete understanding of fluid-melt-rock interactions. The results of the research that follows has important implications for: the role of lower crustal foundering in the geochemical origin and evolution of the modern continental crust (Chapter 2; Guild et al., under review), metasomatic processes involving aqueous metal-carbon complexes in high pressure-temperature subduction zone fluids (Chapter 3; Guild & Shock, 2020), natural hydrous mineral stability at the slab-mantle interface (Chapter 4; Guild, et al., in preparation) and water-undersaturated melting in the sub-arc (Chapter 5; Guild & Till, in preparation).

Volcanic eruptions are serious geological hazards; the aftermath of the explosive eruptions produced at high-silica volcanic systems often results in long-term threats to climate, travel, farming, and human life. To construct models for eruption forecasting, the timescales of events leading up to eruption must be accurately quantified. In the field of igneous petrology, the timing of these events (e.g. periods of magma formation, duration of recharge events) and their influence on eruptive timescales are still poorly constrained.

In this dissertation, I discuss how the new tools and methods I have developed are helping to improve our understanding of these magmatic events. I have developed a method to calculate more accurate timescales for these events from the diffusive relaxation of chemical zoning in individual mineral crystals (i.e., diffusion chronometry), and I use this technique to compare the times recorded by different minerals from the same Yellowstone lava flow, the Scaup Lake rhyolite.

I have also derived a new geothermometer to calculate magma temperature from the compositions of the mineral clinopyroxene and the surrounding liquid. This empirically-derived geothermometer is calibrated for the high FeOtot (Mg# = 56) and low Al2O3 (0.53–0.73 wt%) clinopyroxene found in the Scaup Lake rhyolite and other high-silica igneous systems. A determination of accurate mineral temperatures is crucial to calculate magmatic heat budgets and to use methods such as diffusion chronometry. Together, these tools allow me to paint a more accurate picture of the conditions and tempo of events inside a magma body in the millennia to months leading up to eruption.

Additionally, I conducted petrological experiments to determine the composition of hypothetical exoplanet partial mantle melts, which could become these planets’ new crust, and therefore new surface. Understanding the composition of an exoplanet’s crust is the first step to understanding chemical weathering, surface-atmosphere chemical interactions, the volcanic contribution to any atmosphere present, and biological processes, as life depends on these surfaces for nutrients. The data I have produced can be used to predict differences in crust compositions of exoplanets with similar bulk compositions to those explored herein, as well as to calibrate future exoplanet petrologic models.

I present for the first time a broad-scale assessment of dissolved organic matter in the continental hot springs of Yellowstone National Park. The concentration of dissolved organic carbon in hot springs is highly variable, but demonstrates distinct trends with the geochemical composition of springs. The dissolved organic carbon concentrations are lowest in the hottest, most deeply sourced hot springs. Mixing of hydrothermal fluids with surface waters or reaction with buried sedimentary organic matter is typically indicated by increased dissolved organic carbon concentrations. I assessed the bulk composition of organic matter through fluorescence analysis that demonstrated different fluorescent components associated with terrestrial organic matter, microbial organic matter, and several novel fluorescent signatures unique to hot springs. One novel fluorescence signature is observed exclusively in acidic hot springs, and it is likely an end product of thermally-altered sedimentary organic matter. This acid-spring component precipitates out of solution under neutral or alkaline conditions and characterization of the precipitate revealed evidence for a highly condensed aromatic structure. This acid-spring component serves as a reliable tracer of acidic, hot water that has cycled through the subsurface. Overall, dissolved organic carbon concentrations and fluorescent features correlate with the inorganic indicators traditionally used to infer spring fluid mixing in the subsurface. Further, the fluorescence information reveals subtle differences in mixing between fluid phases that are not distinguishable through classic inorganic indicator species. My work assessing dissolved organic carbon in the Yellowstone National Park hot springs reveals that the organic matter in hydrothermal systems is different from that found in surface waters, and that the concentration and composition of hot spring dissolved organic matter reflects the subsurface geochemical and hydrological environment.

Utilizing both 16S and 18S rRNA sequencing alongside energetic calculations from geochemical measurements offers a bridged perspective of prokaryotic and eukaryotic community diversities and their relationships to geochemical diversity. Yellowstone National Park hot spring outflows from varied geochemical compositions, ranging in pH from < 2 to > 9 and in temperature from < 30°C to > 90°C, were sampled across the photosynthetic fringe, a transition in these outflows from exclusively chemosynthetic microbial communities to those that include photosynthesis. Illumina sequencing was performed to document the diversity of both prokaryotes and eukaryotes above, at, and below the photosynthetic fringe of twelve hot spring systems. Additionally, field measurements of dissolved oxygen, ferrous iron, and total sulfide were combined with laboratory analyses of sulfate, nitrate, total ammonium, dissolved inorganic carbon, dissolved methane, dissolved hydrogen, and dissolved carbon monoxide were used to calculate the available energy from 58 potential metabolisms. Results were ranked to identify those that yield the most energy according to the geochemical conditions of each system. Of the 46 samples taken across twelve systems, all showed the greatest energy yields using oxygen as the main electron acceptor, followed by nitrate. On the other hand, ammonium or ammonia, depending on pH, showed the greatest energy yields as an electron donor, followed by H2S or HS-. While some sequenced taxa reflect potential biotic participants in the sulfur cycle of these hot spring systems, many sample locations that yield the most energy from ammonium/ammonia oxidation have low relative abundances of known ammonium/ammonia oxidizers, indicating potentially untapped sources of chemotrophic energy or perhaps poorly understood metabolic capabilities of cultured chemotrophs.

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.

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.

Many acidic hot springs in Yellowstone National Park support microbial iron oxidation, reduction, or microbial iron redox cycling (MIRC), as determined by microcosm rate experiments. Microbial dissimilatory iron reduction (DIR) was detected in numerous systems with a pH < 4. Rates of DIR are influenced by the availability of ferric minerals and organic carbon. Microbial iron oxidation (MIO) was detected from pH 2 – 5.5. In systems with abundant Fe (II), dissolved oxygen controls the presence of MIO. Rates generally increase with increased Fe(II) concentrations, but rate constants are not significantly altered by additions of Fe(II). MIRC was detected in systems with abundant ferric mineral deposition.

The rates of microbial and abiological iron oxidation were determined in a variety of cold (T= 9-12°C), circumneutral (pH = 5.5-9) environments in the Swiss Alps. Rates of MIO were measured in systems up to a pH of 7.4; only abiotic processes were detected at higher pH values. Iron oxidizing bacteria (FeOB) were responsible for 39-89% of the net oxidation rate at locations where biological iron oxidation was detected. Members of putative iron oxidizing genera, especially Gallionella, are abundant in systems where MIO was measured. Speciation calculations reveal that ferrous iron typically exists as FeCO30, FeHCO3+, FeSO40 or Fe2+ in these systems. The presence of ferrous (bi)carbonate species appear to increase abiotic iron oxidation rates relative to locations without significant concentrations. This approach, integrating geochemistry, rates, and community composition, reveals biogeochemical conditions that permit MIO, and locations where the abiotic rate is too fast for the biotic process to compete.

For a reaction to provide habitability for microbes in a given environment, it must energy yield and this energy must dissipate slowly enough to remain bioavailable. Thermodynamic boundaries exist at conditions where reactions do not yield energy, and can be quantified by calculations of chemical energy. Likewise, kinetic boundaries exist at conditions where the abiotic reaction rate is so fast that reactants are not bioavailable; this boundary can be quantified by measurements biological and abiological rates. The first habitability maps were drawn, using iron oxidation as an example, by quantifying these boundaries in geochemical space.