Evaluations of chemical energy supplies for redox reactions used by chemotrophs in water-rock hosted ecosystems are often done separately from evaluations of chemotroph diversity. However, given that energy is a fundamental and unifying parameter for life, much can be gained by evaluating chemical energy as an ecological parameter of water-rock hosted ecosystems. Therefore, I developed an approach that combines evaluation of chemical energy supplies with 16S and 18S rRNA gene amplicon sequencing. I used this approach to assess drivers of microbial distribution, diversity and activity in serpentinized fluids of the Samail Ophiolite of Oman and in hot springs in Yellowstone National Park.

Through the application of the approach, microbiological interactions in serpentinized fluids were found to be more complex than anticipated. Serpentinized fluids are hyperalkaline and pH is often considered the driving parameter of microbial diversity, however hydrogenotrophic community composition varies in hyperalkaline fluids with similar pH. The composition of hydrogenotrophic communities in serpentinized fluids were found to correspond to the availability of the electron acceptor for hydrogenotrophic redox reactions. Specifically, hydrogenotrophic community composition transitions from being dominated by the hydrogenotrophic methanogen genus, Methanobacterium, when the concentration of sulfate is less than ~10 μm. Above ~10 μm, sulfate reducers are most abundant. Additionally, Methanobacterium was found to co-occur with the protist genus, Cyclidium, in serpentinized fluids. Species of Cyclidium are anaerobic and known to have methanogen endosymbionts. Therefore, Cyclidium may supply inorganic carbon evolved from fermentation to Methanobacterium, thereby mitigating pH dependent inorganic carbon limitation.

This approach also revealed possible biological mechanisms for methane oxidation in Yellowstone hot springs. Measurable rates of biological methane oxidation in hot spring sediments are likely associated with methanotrophs of the phylum, Verrucomicrobia, and the class, Alphaproteobacteria. Additionally, rates were measurable where known methanotrophs were not detected. At some of these sites, archaeal ammonia oxidizer taxa were detected. Ammonia oxidizers have been shown to be capable of methane oxidation in other systems and may be an alternative mechanism for methanotrophy in Yellowstone hot springs. At the remaining sites, uncharacterized microbial lineages may be capable of carrying out methane oxidation in Yellowstone hot springs.

Tempe Town Lake is the site of fifteen years’ worth of chemical data collection by ASU researchers. In 2018 the dataSONDE, an instrument capable of measuring different water quality parameters every thirty minutes for a month at a time was installed in the lake. The SONDE has the potential to completely reduce the need for sampling by hand. Before the SONDE becomes the sole means of gathering data, it is important to verify its accuracy. In this study, the measurements gathered by the SONDE (pH, dissolved oxygen, temperature, conductivity and colored dissolved organic matter) were compared to measurements gathered using the verified methods from the past fifteen years.

Volcanic eruptions can be serious geologic hazards, and have the potential to effect human life, infrastructure, and climate. Therefore, an understanding of the evolution and conditions of the magmas stored beneath volcanoes prior to their eruption is crucial for the ability to monitor such systems and develop effective hazard mitigation plans. This dissertation combines classic petrologic tools such as mineral chemistry and thermometry with novel techniques such as diffusion chronometry and statistical modeling in order to better understand the processes and timing associated with volcanic eruptions. By examining zoned crystals from the fallout ash of Yellowstone’s most recent supereruption, my work shows that the rejuvenation of magma has the ability to trigger a catastrophic supereruption at Yellowstone caldera in the years (decades at most) prior to eruption. This provides one of the first studies to thoroughly identify a specific eruption trigger of a past eruption using the crystal record. Additionally, through experimental investigation, I created a novel diffusion chronometer with application to determine magmatic timescales in silicic volcanic systems (i.e., rhyolite/dacite). My results show that Mg-in-sanidine diffusion operates simultaneously by both a fast and slow diffusion path suggesting that experimentally-derived diffusion chronometers may be more complex than previously thought. When applying Mg-in-sanidine chronometry to zoned sanidine from the same supereruption at Yellowstone, the timing between rejuvenation and eruption is further resolved to as short as five months, providing a greater understanding of the timing of supereruption triggers. Additionally, I developed a new statistical model to examine the controls on a single volcano’s distribution of eruptions through time, therefore the controls on the timing between successive eruptions, or repose time. When examining six Cascade volcanoes with variable distribution patterns through time, my model shows these distributions are not result of sampling bias, rather may represent geologic processes. There is a robust negative correlation between average repose time and average magma composition (i.e., SiO2), suggesting this may be a controlling factor of long-term repose time at Cascade volcanoes. Together, my work provides a better vision for forecasting models to mitigate potential destruction.

Organic compounds are influenced by hydrothermal conditions in both marine and terrestrial environments. Sedimentary organic reservoirs make up the largest share of organic carbon in the carbon cycle, leading to petroleum generation and to chemoautotrophic microbial communities. There have been numerous studies on the reactivity of organic compounds in water at elevated temperatures, but these studies rarely explore the consequences of inorganic solutes in hydrothermal fluids. The experiments in this thesis explore new reaction pathways of organic compounds mediated by aqueous and solid phase metals, mainly Earth-abundant copper. These experiments show that copper species have the potential to oxidize benzene and toluene, which are typically viewed as unreactive. These pathways add to the growing list of known organic transformations that are possible in natural hydrothermal systems. In addition to the characterization of reactions in natural systems, there has been recent interest in using hydrothermal conditions to facilitate organic transformations that would be useful in an applied, industrial or synthetic setting. This thesis identifies two sets of conditions that may serve as alternatives to commonplace industrial processes. The first process is the oxidation of benzene with copper to form phenol and chlorobenzene. The second is the copper mediated dehalogenation of aryl halides. Both of these processes apply the concepts of geomimicry by carrying out organic reactions under Earth-like conditions. Only water and copper are needed to implement these processes and there is no need for exotic catalysts or toxic reagents.

Due to analytical limitations, thermodynamic modeling is a lucrative alternative for obtaining metal speciation in chemically complex systems like life. However, such modeling is limited by the lack of equilibrium constant data for metal-complexation reactions, particularly for metal-organic species. These problems were ameliorated estimating these properties from 0-125°C for ~18,000 metal complexes of small molecules, proteins and peptides.

The estimates of metal-ligand equilibrium constants at 25°C and 1 bar were made using multiple linear free energy relationships in accordance with the metal-coordinating properties of ligands such as denticity, identity of electron donor group, inductive effects and steric hindrance. Analogous relationships were made to estimated metal-ligand complexation entropy that facilitated calculation of equilibrium constants up to 125°C using the van’t Hoff equation. These estimates were made for over 250 ligands that include carboxylic acids, phenols, inorganic acids, amino acids, peptides and proteins.

The stability constants mentioned above were used to obtain metal speciation in several microbial growth media including past bioavailability studies and compositions listed on the DSMZ website. Speciation calculations were also carried out for several metals in blood plasma and cerebrospinal fluid that include metals present at over micromolar abundance (sodium, potassium, calcium, magnesium, iron, copper and zinc) and metals of therapeutic or toxic potential (like gallium, rhodium and bismuth). Metal speciation was found to be considerably dependent on pH and chelator concentration that can help in the selection of appropriate ligands for gallium & rhodium based anticancer drugs and zinc-based antidiabetics. It was found that methanobactin can considerably alter copper speciation and is therefore a suitable agent for the treatment of Wilson Disease. Additionally, bismuth neurotoxicity was attributed to the low transferrin concentration in cerebrospinal fluid and the predominance of aqueous bismuth trihydroxide. These results demonstrate that metal speciation calculations using thermodynamic modeling can be extremely useful for understanding metal bioavailability in microbes and human bodily fluids.

Dissolved organic matter (DOM) can have numerous effects on the water chemistry and the biological life within an aquatic system with its wide variety of chemical structures and properties. The composition of the dissolved carbon can be estimated by utilizing the fluorescent properties of some DOM such as aromatic amino acids and humic material. This experiment was used to observe how organic matter could influence hydrothermal systems, such as Sylvan Springs in Yellowstone National Park, USA. Using optical density at 600 nm (OD 600), excitation-emission matrix spectra (EEMS), and Illumina sequencing methods (16S rRNA gene sequencing), changes in dissolved organic matter (DOM) were observed based on long term incubation at 84ºC and microbial influence. Four media conditions were tested over a two-month duration to assess these changes: inoculated pine needle media, uninoculated pine needle media, inoculated yeast extract media, and uninoculated yeast extract media. The inoculated samples contained microbes from a fluid and sediment sample of Sylvan Spring collected July 23, 2018. Absorbance indicated that media containing pine needle broth poorly support life, whereas media containing yeast extract revealed a positive increase in growth. Excitation-Emission Matrix Spectra of the all media conditions indicated changes in DOM composition throughout the trial. There were limited differences between the inoculated and uninoculated samples suggesting that the DOM composition change in this study was dominated by the two-month incubation at 84ºC more than biotic processes. Sequencing performed on a sediment sample collected from Sylvan Spring indicated five main order of prokaryotic phyla: Aquificales, Desulfurococcales, Thermoproteales, Thermodesulfobacteriales, and Crenarchaeota. These organisms are not regarded as heterotrophic microbes, so the lack of significant biotic changes in DOM could be a result of these microorganisms not being able to utilize these enrichments as their main metabolic energy supply.

Ethnogeology is the scientific study of human relationships with the Earth as a system, typically conducted within the context of a specific culture. Indigenous or historically resident people may perceive local places differently from outside observers trained in the Western tradition. Ethnogeologic knowledge includes traditional indigenous knowledge (alternatively referred to as traditional ecological knowledge or TEK), which exceeds the boundaries of non-Indigenous ideas of physical characteristics of the world, tends to be more holistic, and is culturally framed. In this ethnogeological study, I have implemented several methods of participatory rapid assessment (PRA) from the discipline of field ethnography to collect culturally framed geological knowledge, as well to measure the authenticity of the knowledge collected. I constructed a cultural consensus model (CCM) about karst as a domain of knowledge. The study area is located in the karst physiographic region of the Caribbean countries of the Dominican Republic (DR) and Puerto Rico (PR). Ethnogeological data collected and analyzed using CCM satisfied the requirements of a model where I have found statistically significance among participant’s agreement and competence values. Analysis of the competence means in the population of DR and PR results in p < 0.05 validating the methods adapted for this study. I discuss the CCM for the domain of karst (in its majority) that is shared among consultants in the countries of PR and the DR that is in the form of metaphors and other forms of culturally framed descriptions. This work continuing insufficient representation of minority groups such as Indigenous people, Native Americans, Alaska Natives, and Hispanic/Latinxs in the Earth Sciences.

Atmospheric particulate matter (PM) has a pronounced effect on our climate, and exposure to PM causes negative health outcomes and elevated mortality rates in urban populations. Reactions that occur in fog can form new secondary organic aerosol material from gas-phase species or primary organic aerosols. It is important to understand these reactions, as well as how organic material is scavenged and deposited, so that climate and health effects can be fully assessed. Stable carbon isotopes have been used widely in studying gas- and particle-phase atmospheric chemistry. However, the processing of organic matter by fog has not yet been studied, even though stable isotopes can be used to track all aspects of atmospheric processing, from particle formation, particle scavenging, reactions that form secondary organic aerosol material, and particle deposition. Here, carbon isotope analysis is used for the first time to assess the processing of carbonaceous particles by fog.

This work first compares carbon isotope measurements (δ13C) of particulate matter and fog from locations across the globe to assess how different primary aerosol sources are reflected in the atmosphere. Three field campaigns are then discussed that highlight different aspects of PM formation, composition, and processing. In Tempe, AZ, seasonal and size-dependent differences in the δ13C of total carbon and n-alkanes in PM were studied. δ13C was influenced by seasonal trends, including inversion, transport, population density, and photochemical activity. Variations in δ13C among particle size fractions were caused by sources that generate particles in different size modes.

An analysis of PM from urban and suburban sites in northeastern France shows how both fog and rain can cause measurable changes in the δ13C of PM. The δ13C of PM was consistent over time when no weather events occurred, but particles were isotopically depleted by up to 1.1‰ in the presence of fog due to preferential scavenging of larger isotopically enriched particles. Finally, the δ13C of the dissolved organic carbon in fog collected on the coast of Southern California is discussed. Here, temporal depletion of the δ13C of fog by up to 1.2‰ demonstrates its use in observing the scavenging and deposition of organic PM.

Lipids perform functions essential to life and have a variety of structures that are influenced by the organisms and environments that produced them. Lipids tend to resist degradation after cell death, leading to their widespread use as biomarkers in geobiology, though their interpretation is often tricky. Many lipid structures are shared among organisms and function in many geochemical conditions and extremes. I argue it is useful to interpret lipid distributions as a balance of functional necessity and energy cost. This work utilizes a quantitative thermodynamic framework for interpreting energetically driven adaptation in lipids.

Yellowstone National Park is a prime location to study biological adaptations to a wide range of temperatures and geochemical conditions. Lipids were extracted and quantified from thermophilic microbial communities sampled along the temperature (29-91°C) and chemical gradients of four alkaline Yellowstone hot springs. I observed that decreased alkyl chain carbon content, increased degree of unsaturation, and a shift from ether to ester linkage caused a downstream increase in the average oxidation state of carbon (ZC) I hypothesized these adaptations were selected because they represent cost-effective solutions to providing thermostable membranes.

This hypothesis was explored by assessing the relative energetic favorability of autotrophic reactions to form alkyl chains from known concentrations of dissolved inorganic species at elevated temperatures. I found that the oxidation-reduction potential (Eh) predicted to favor formation of sample-representative alkyl chains had a strong positive correlation with Eh calculated from hot spring water chemistry (R2 = 0.72 for the O2/H2O redox couple). A separate thermodynamic analysis of bacteriohopanepolyol lipids found that predicted equilibrium abundances of observed polar headgroup distributions were also highly correlated with Eh of the surrounding water (R2= 0.84). These results represent the first quantitative thermodynamic assessment of microbial lipid adaptation in natural systems and suggest that observed lipid distributions represent energetically cost-effective assemblages along temperature and chemical gradients.

Carboxylic acids are an abundant and reactive species present throughout our solar system. The reactions of carboxylic acids can shape the organic abundances within oil field brines, carbonaceous chondrites, and different ranks of coal.

I have performed hydrothermal experiments with model aromatic carboxylic acids in the presences of different oxide minerals to investigate the reactions available to carboxylic acids in the presence of mineral surfaces. By performing experiments containing one organic compound and one mineral surface, I can begin to unravel the different reactions that can occur in the presence of different minerals.

I performed experiments with phenylacetic acid (PAA), hydrocinnamic acid (HCA) and benzoic acid (BA) in the presence of spinel (MgAl2O4), magnetite (Fe3O4), hematite (Fe2O3), and corundum (Al2O3). The focus of this work was metal oxide minerals, with and without transition metal atoms, and with different crystal structures. I found that all four oxide minerals facilitated ketonic decarboxylation reactions of carboxylic acids to form ketone structures. The two minerals containing transition metals (magnetite and hematite) also opened a reaction path involving electrochemical oxidation of one carboxylic acid, PAA, to the shorter chain version of a second carboxylic acid, BA, in experiments starting with PAA. Fundamental studies like these can help to shape our knowledge of the breadth of organic reactions that are possible in geologic systems and the mechanisms of those reactions.