The Effect of Wood Burial and Submersion on Decomposition: Implications for Reducing Carbon Emissions

Gemstone Team Carbon Sinks

Geochemistry of crustal formation and evolution

Terrestrial planets produce crusts as they differentiate. The Earth’s bi-modal crust, with a high-standing granitic continental crust and a low-standing basaltic oceanic crust, is unique in our solar system and links the evolution of the interior and exterior of this planet. Here I present geochemical observations to constrain processes accompanying crustal formation and evolution. My approach includes geochemical analyses, quantitative modeling, and experimental studies. The Archean crustal evolution project represents my perspective on when Earth’s continental crust began forming. In this project, I utilized critical element ratios in sedimentary records to track the evolution of the MgO content in the upper continental crust as a function time. The early Archean subaerial crust had >11 wt. % MgO, whereas by the end of Archean its composition had evolved to about 4 wt. % MgO, suggesting a transition of the upper crust from a basalt-like to a more granite-like bulk composition. Driving this fundamental change of the upper crustal composition is the widespread operation of subduction processes, suggesting the onset of global plate tectonics at ~ 3 Ga (Abstract figure). Three of the chapters in this dissertation leverage the use of Eu anomalies to track the recycling of crustal materials back into the mantle, where Eu anomaly is a sensitive measure of the element’s behavior relative to neighboring lanthanoids (Sm and Gd) during crustal differentiation. My compilation of Sm-Eu-Gd data for the continental crust shows that the average crust has a net negative Eu anomaly. This result requires recycling of Eu-enriched lower continental crust to the mantle. Mass balance calculations require that about three times the mass of the modern continental crust was returned into the mantle over Earth history, possibly via density-driven recycling. High precision measurements of Eu/Eu* in selected primitive glasses of mid-ocean ridge basalt (MORB) from global MORs, combined with numerical modeling, suggests that the recycled lower crustal materials are not found within the MORB source and may have at least partially sank into the lower mantle where they can be sampled by hot spot volcanoes. The Lesser Antilles Li isotope project provides insights into the Li systematics of this young island arc, a representative section of proto-continental crust. Martinique Island lavas, to my knowledge, represent the only clear case in which crustal Li is recycled back into their mantle source, as documented by the isotopically light Li isotopes in Lesser Antilles sediments that feed into the fore arc subduction trench. By corollary, the mantle-like Li signal in global arc lavas is likely the result of broadly similar Li isotopic compositions between the upper mantle and bulk subducting sediments in most arcs. My PhD project on Li diffusion mechanism in zircon is being carried out in extensive collaboration with multiple institutes and employs analytical, experimental and modeling studies. This ongoing project, finds that REE and Y play an important role in controlling Li diffusion in natural zircons, with Li partially coupling to REE and Y to maintain charge balance. Access to state-of-art instrumentation presented critical opportunities to identify the mechanisms that cause elemental fractionation during laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis. My work here elucidates the elemental fractionation associated with plasma plume condensation during laser ablation and particle-ion conversion in the ICP.

Evolution of strength and physical properties of ultramafic and carbonate rocks under hydrothermal conditions

Interaction of rocks with fluids can significantly change mineral assemblage and structure. This so-called hydrothermal alteration is ubiquitous in the Earth’s crust. Though the behavior of hydrothermally altered rocks can have planet-scale consequences, such as facilitating oceanic spreading along slow ridge segments and recycling volatiles into the mantle at subduction zones, the mechanisms involved in the hydrothermal alteration are often microscopic. Fluid-rock interactions take place where the fluid and rock meet. Fluid distribution, flux rate and reactive surface area control the efficiency and extent of hydrothermal alteration. Fluid-rock interactions, such as dissolution, precipitation and fluid mediated fracture and frictional sliding lead to changes in porosity and pore structure that feed back into the hydraulic and mechanical behavior of the bulk rock. Examining the nature of this highly coupled system involves coordinating observations of the mineralogy and structure of naturally altered rocks and laboratory investigation of the fine scale mechanisms of transformation under controlled conditions. In this study, I focus on fluid-rock interactions involving two common lithologies, carbonates and ultramafics, in order to elucidate the coupling between mechanical, hydraulic and chemical processes in these rocks. I perform constant strain-rate triaxial deformation and constant-stress creep tests on several suites of samples while monitoring the evolution of sample strain, permeability and physical properties. Subsequent microstructures are analyzed using optical and scanning electron microscopy. This work yields laboratory-based constraints on the extent and mechanisms of water weakening in carbonates and carbonation reactions in ultramafic rocks. I find that inundation with pore fluid thereby reducing permeability. This effect is sensitive to pore fluid saturation with respect to calcium carbonate. Fluid inundation weakens dunites as well. The addition of carbon dioxide to pore fluid enhances compaction and partial recovery of strength compared to pure water samples. Enhanced compaction in CO2-rich fluid samples is not accompanied by enhanced permeability reduction. Analysis of sample microstructures indicates that precipitation of carbonates along fracture surfaces is responsible for the partial restrengthening and channelized dissolution of olivine is responsible for permeability maintenance.

EXPERIMENTAL DEMONSTRATION OF LIGHT TRAPPING AND INTERNAL LIGHT SCATTERING IN SOLAR CELLS

Renewable energy technologies have long-term economic and environmental advantages over fossil fuels, and solar power is the most abundant renewable resource, supplying 120 PW over earth’s surface. In recent years the cost of photovoltaic modules has reached grid parity in many areas of the world, including much of the USA. A combination of economic and environmental factors has encouraged the adoption of solar technology and led to an annual growth rate in photovoltaic capacity of 76% in the US between 2010 and 2014. Despite the enormous growth of the solar energy industry, commercial unit efficiencies are still far below their theoretical limits. A push for thinner cells may reduce device cost and could potentially increase device performance. Fabricating thinner cells reduces bulk recombination, but at the cost of absorbing less light. This tradeoff generally benefits thinner devices due to reduced recombination. The effect continues up to a maximum efficiency where the benefit of reduced recombination is overwhelmed by the suppressed absorption. Light trapping allows the solar cell to circumvent this limitation and realize further performance gains (as well as continue cost reduction) from decreasing the device thickness. This thesis presents several advances in experimental characterization, theoretical modeling, and device applications for light trapping in thin-film solar cells. We begin by introducing light trapping strategies and discuss theoretical limits of light trapping in solar cells. This is followed by an overview of the equipment developed for light trapping characterization. Next we discuss our recent work measuring internal light scattering and a new model of scattering to predict the effects of dielectric nanoparticle back scatterers on thin-film device absorption. The new model is extended and generalized to arbitrary stacks of stratified media containing scattering structures. Finally, we investigate an application of these techniques using polymer dispersed liquid crystals to produce switchable solar windows. We show that these devices have the potential for self-powering.