Title: On the physics and chemistry of carbon dioxide capture and storage in terrestrial and marine environments
Description: The production of CO 2 from the oxidation of fossil-carbon over the past 200 years has resulted in the accumulation of CO 2 in the atmosphere. In the atmosphere, CO 2 --like other greenhouse gases--slows the rate at which radiation is emitted from the Earth. By increasing the concentration of CO 2 in the atmosphere, humanity is altering the Earth's radiation balance in a potentially dangerous way. Mitigating humanity's impact on the Earth's climate system requires transforming the global energy infrastructure to decrease anthropogenic emissions of CO 2 . The body of work presented here covers a range of physical and chemical topics important for the mitigation of anthropogenic climate change through the capture and storage of CO 2 . This dissertation is focused primarily on addressing CO 2 emissions from large stationary point-sources through CO 2 capture and storage (CCS). A portion of the work, however, is aimed at addressing the long tail of the CO 2 point-sources distribution by removing CO 2 directly from the atmosphere. The entire CCS supply chain from the thermodynamic limit of the work required to capture CO 2 from power-plants to the long-term chemical and physical evolution of CO 2 that has been injected into geologic repositories is evaluated with the use numerical models as well as thermodynamic and energetic calculations. In addition, a method to engineer the carbon cycle as an approach to address the long tail of the CO 2 -point-source distribution was developed. In all five of the chapters, the study of energetics plays an important role. Chapter 2 applies thermodynamics to derive an analytic relationship for the CCS energy penalty, and several valuable insights are ascertained from that relationship.

The central insight of chapter 3--that a geologic formation's ability to dissipate induced pressure is often the limiting resource of CO 2 storage--derives from energetic models of compressive flow in porous media. The primary contribution of chapter 4 is the notion that in a certain thermodynamic phase space, liquid CO 2 is denser than seawater, and thus it can be gravitationally trapped in deepsea sediments. Chapter 5 extends chapter 4's analysis of state properties to a larger pressure and temperature range. Finally, chapter 6 describes the energetics of accelerating chemical weathering with electrochemistry.