Title: Models of Reactive-Brittle Dynamics in the Earth's Lithosphere with Applications to Hydration and Carbonation of Mantle Peridotite
Description: Ultramafic rocks – that are usually located deep below the Earth's surface – are occasionally exhumed by the motion of tectonic plates. The massive chemical disequilibrium that exists between these exposed rocks and the surface waters and atmosphere leads to geologically rapid reactions that consume water and CO₂, binding them to form secondary hydrated/carbonated solid minerals that are found extensively in continental exposures (ophiolites) and at the seafloor near mid-ocean ridges. Pervasive fracturing and faulting in oceanic lithosphere generates pathways for fluids to access and react with rocks that are in some cases located down to depths of tens of kilometers. Over time, the large volumes of fluids and volatiles that are bound up in crustal and upper mantle rocks via such reactions are eventually subducted to extreme depths where subsequent fluid release can trigger melting, arc volcanism and seismic activity. In addition to their geophysical importance, these reactions are also considered to be critical for the survival of organisms in deep sea hydrothermal systems, and a potential source in the origin of life hypothesis.

The natural transfer of atmospheric CO₂ to stable, solid carbonate minerals has, in recent years, motivated a large research effort towards investigating its potential as a large-scale carbon sequestration alternative. Understanding the geophysical impact and environmental potential of these reactions and their related processes requires knowledge of their basic physical and chemical behavior. Because of the difficulties of observing these processes in real-time, either experimentally or in the field, there has been a heavy reliance on hypothetical arguments that have been driven by observations in natural rocks. The observations paint a very complex picture – involving an interplay between reaction, fluid flow and fracturing – that is not easily explained by simple model descriptions. Although there has been increasing interest in modeling this class of problems in recent years, to date there remains a considerable gap between the theory and computational framework that is required for a consistent model description.

A major theme in said models is their omission of poro-mechanical effects and complications arising from clogging of pore space with precipitating minerals. Both of these are necessary ingredients for a consistent model; however, they require a more complex description that is based on coupled multiphase continuum mechanics, reactive transport, and potentially brittle failure. Each of these components is a technical challenge in its own right, requiring development of novel theory and computation that integrates them in a suitable manner. The overall goals and themes of this thesis are aimed at closing this gap. To this end, I develop a modeling framework and computational tools that are capable of describing reactive flow in brittle media, with a specific focus on fluid-mineral reactions in near-surface ultramafic rock environments. The exposition of this framework is split into 3 separate chapters that build on one other in increments of complexity. Specifically, Chapter 1 presents a poromechanics-based description of coupled fluid flow, mass transfer and solid deformation for a simplified hydration reaction.

This model is extended in Chapter 2 to incorporate cracking by adopting modern developments in computational fracture mechanics. Finally, in Chapter 3 I extend the set of reactions to support mixed H₂O-CO₂ fluids by leveraging recently developed tools in computational thermodynamics. Along the way I present a number of numerical model simulations that develop intuition and draw comparisons with natural observations, whilst remaining mindful of its limitations and areas for improvement. Overall, this work represents progress towards better understanding of physical and chemical feedbacks of reactive-brittle processes in the Earth's near-surface and the potential for large-scale carbon sequestration.