abstract: 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. / Dissertation/Thesis / Doctoral Dissertation Geological Sciences 2020

The production of hydrogen (H2) and methane (CH4) related to olivine hydration (i.e. serpentinization) is considered a major contributor to abiotic hydrocarbon synthesis on Earth. Recent discoveries have highlighted the importance of low temperature (<100oC) serpentinization at continental peridotite outcrops. Such sites produce substantial fluxes of abiotic CH4 from gas seeps and/or springs. A limited number of studies in the southern hemisphere offer research on low temperature abiotic hydrocarbon synthesis in natural ultramafic environments, though large areas of exposed ophiolite are prevalent. This study assesses the origin and flux of CH4 and related water-rock interactions from a previously undiscovered site in the Dun Mountain Ophiolite Belt (DMOB), located at Red Hills, New Zealand. Methane emissions from a hyper-alkaline (pH >11.6) and reduced spring of calcium hydroxide (Ca2+-OH-) type waters near the Maitlands Fault were between 730 to 17,000 mg m 2day 1. The δ13C and δD values of CH4 emitting from this spring are consistent with CH4 of abiotic origin (δ13C: 32.7 ‰ VPDB, δD: 363 ‰ V SMOW). Hyper-alkaline fluids emitting from the spring are concentrated in dissolved CH4 (2.2 mg/L) and H2 (0.7 mg/L) and display δ13CCH4 signatures consistent with other sites worldwide. Extensive and localised carbonate precipitation occurs at the hyper-alkaline Ca-rich spring. Isotopic evaluation of carbonate nodules are kinetically fractionated with 13C and 18O depletions up to 30.8 ‰ and 9.3 ‰, respectively. This disequilibrium between the mineralogy and interacting fluids and gases represents a potential habitable environment for microorganisms. Porous, layered carbonates located on the outer edges of the hyper-alkaline spring are the result of atmospheric CO2 interaction with magnesium bicarbonate (Mg2+-HCO3) and Ca2+-OH- hyper-alkaline waters. The precipitation of these carbonates offers potential insight towards low temperature CO2 sequestration. Additionally, various forms of Fe-rich amorphous material precipitate in association with Mg2+-HCO3 type waters at the Red Hills. The identification of bacteria and diatoms within this material offers supporting information regarding microbial survival in metal-rich, reduced environments. This multidisciplinary study demonstrates the interconnected nature of geological, biological and atmospheric interactions in ultramafic environments at low temperature on Earth.