Thesis (D.Phil.)--University of Oxford, 2009. / Supervisor: Professor Gordon L. Clark. Bibliography: leaves 239-260.

Thesis (M.S.) -- Mississippi State University. Dave C. Swalm School of Chemical Engineering. / Title from title screen. Includes bibliographical references.

Thesis (Ph.D.)--University of Wyoming, 2009. / Title from PDF title page (viewed on May 21, 2010). Includes bibliographical references (p. 50-63).

Thesis (Ph. D.)--Ohio State University, 2007. / Title from first page of PDF file. Includes bibliographical references (p. 149-154).

As energy use increases globally the environmental burdens increase alike. Many accusations have been made that carbon dioxide is a culprit of climate change. The University of Kentucky and Duke Energy Power have partnered to test carbon capture technology in a large scale project. To this end, the objective of this thesis is to investigate potential water media sources and nutrient sources at different volume scales for algae cultivation to help create a more environmentally viable and economically feasible solution. This work will conduct a life cycle assessment of water media sources and the effects of the inputs and outputs needed for each medium. The up-scaling objective of the research is to identify which parameters vary as a result of up-scaling and how to maintain a culture at the large scale that is standardized to the lab scale culture.

In order to increase energy security and meet carbon emission reduction targets set by the EU and UK government, the UK energy sector has increased its reliance on renewable energy. The marine renewable sector is set to become a major contributor to the UK's energy portfolio but incumbent on the offshore renewable sector are the high development, operation and maintenance costs. Prevailing metocean conditions at an offshore energy site contribute significantly to the life-cycle costs of an offshore energy project. Where access to a site is limited by a lack of suitable weather-windows, leading to high instances of downtime, weather-induced costs increase. Determination of suitable metocean weather-windows, defined by maximum operating thresholds and the length of time required to perform a task can assist with the risk management of a project and the reduction of downtimes, thus reducing costs. Metocean weather-windows are determined using 31 years (the “climatological norm”) of ECMWF ERA-40 reanalysis data. The annual, seasonal and monthly distribution parameters for wind and wave regimes at three sites are derived, using three different distribution parameter estimation models. Probabilities of defined weather-windows are determined using the derived distribution parameters and compared with empirical probabilities, based on the frequentist approach. Wind regimes fit a Weibull distribution and wave regimes fit a 3P gamma distribution and unique annual, seasonal and monthly distribution parameters are required for accurate weather-window determination. When fitted to appropriate PDFs, the shape and scale values determined by the different estimation techniques result in significantly different probabilities. Empirical probabilities converge with those determined using the MLE model but both significantly differ from those derived using the LSM and MoM derived parameters. In the absence of a dataset spanning the climatological norm, this suggests that the MLE method of parameter estimation is more accurate for the successful determination of weather-windows.

Albany thicket is prevalent in the Eastern Cape Province of South Africa. Its spread has diminished through overgrazing and heavy browsing by animals, land clearance and urban expansion. The result is highly degraded land characterized by invasion of alien species. There is a wealth of documented evidence on the high carbon sequestration ability of thicket biome, but not much has been done to assess its effect on carbon dioxide emissions from the soil. Given that the concentration of atmospheric greenhouse gases has been constantly rising since the industrial era, it is imperative to assess the influence of thicket biome as a source or sink of these gases. There is evidence of shifts in the climate in southern Africa as reflected by changes in rainfall patterns, increased temperatures, recurrent droughts and fires. As such, the historical rainfall variability in an Albany thicket region and its interaction with the temporal land use / cover changes was studied. This served to give some background information about the study area for more detailed study on C and carbon dioxide effluxes in thicket vegetation under different levels of degradation. This study thus aimed to determine the influence of thicket vegetation at various levels of degradation on soil carbon and carbon dioxide fluxes. The impact of plant photosynthetic pathway on soil C residence time and gas effluxes were analysed to elucidate on the land-use and cover patterns occurring in the area. All this was done to shed some light on the role of soil and thicket vegetation on carbon dioxide emissions and C storage in the spectrum of a shifting climate. The main area of research was Amakhala reserve in an Albany thicket in Eastern Cape Province; and it concentrated on three land cover types namely intact thicket, degraded thicket and grassland. The objectives mentioned above were achieved by assessing historical rainfall variability from 1970 to 2010 through trend and time series analysis at nine rainfall stations located at Amakhala reserve, Grahamstown, Bathurst, Port Alfred, Uitenhage and Port Elizabeth. The land use changes that have occurred in the Albany thicket region covering Amakhala reserve, Grahamstown, Bathurst and Port Alfred were also assessed for 1989, 1999 and 2009 through satellite image analysis with Idrisi Andes GIS software; then their interaction with rainfall variability were determined. To elucidate on the vegetation species composition and land use / cover changes that have occurred in the study area, plant biomass as well carbon (C) and nitrogen (N) isotope measurements were done. Plant biomass was assessed for the dominant species through use of pre-existing allometric equations that required data on plant basal diameter, canopy area, stem numbers and height. The plant carbon was then estimated through use of a conversion factor of 0.48 on above-ground biomass, while soil organic C was determined through the modified Walkely - Black method. Carbon and N isotope ratios were determined from the foliar material of three replicate samples of dominant plant species then analyzed through mass spectrometry. Soil carbon dioxide effluxes were then monitored in each of the intact thicket (IT), degraded thicket (DT) and grassland (G) over a 10 month period; by measuring the net carbon dioxide exchange rate (NCER) through the dynamic chamber method. An automated carbon dioxide exchange analyzer, coupled to a soil temperature probe and photosynthetic active radiation (PAR) sensor was used; with NCER measurements taken every 20-30 days. Soil temperature, moisture, penetration resistance and PAR readings were taken during each assay and later used to interpret the NCER. Results showed that long term variability in annual rainfall had a declining trend at Grahamstown (r = -0.59), Uitenhage and Bathurst stations (r = -0.32 at both stations), but was not significant at Amakhala, Port Alfred and Port Elizabeth stations. Most reductions in rainfall occurred in the 1980s and 1990s with the autumn, winter and summer rainfalls, the daily rainfall index and the daily rainfall subclasses of 10 mm and above showing a similar trend. The land use change detection gave a significant increase in proportion of degraded and transformed (moderately degraded) land between 1989 and 2009 with most of the increases occurring from 1989 to 1999, while farmland area decreased by 1.8 percent over the years. Thus the Albany region had over 30 percent of its land occupied by transformed vegetation, with heavy browsing and uncontrolled grazing being attributed to the destruction of pristine vegetation. Land-use change to game ranching and goat pastoralism was attributed to the reduction in farmland. Rainfall variability – land use change linkages were most significant in 1999 that recorded the least rainfall and had the lowest mean, maximum and sum of the NDVI. Grahamstown had the most significant rainfall-NDVI trends as it had the lowest NDVIs in 1999 when rainfall was lowest, the highest NDVI in 1989 when rainfall was highest and moderate NDVIs in 2009 when rainfall was moderate. Vegetation at the IT was characterized by a dense thicket with diverse growth forms of canopy trees, woody shrubs, succulent shrubs and ephemerals which mostly had the C3 type of pathway. This was in contrast with the IT soil isotopy that showed more positive C isotope ratios, indicating a switch between C3 and CAM photosynthesis in original vegetation. Most of the canopy trees had disappeared in the DT to be replaced by herbs, shrubs and grasses. As such, there was a huge difference in isotope ratios between DT plants and soils with the plants having mostly C3 metabolism while the soil showed a predominance of CAM plants in previous vegetation, indicating significant changes in land cover. The G site mostly comprised the grasses Themeda triandra and Panicum maximum and a few herbs. It maintained a dominance of C4 metabolism in both plants and soils showing very little change in species composition over the years. Because of the higher species diversity at IT, its soil organic C was quite high reaching levels of 3.4 percent (i.e. 3.4 t C / ha) in the top 10 cm then decreasing with depth (p < 0.001); but was moderate at DT (1.1-1.3 percent) and very low at G ( 0.5 percent C) (p < 0.001). In the same manner above-ground biomass was highest at IT i.e. 330 000 kg/ha; but was only 22 000 kg/ha in DT and as low as 6 700 kg/ha in G vegetation. High biomass at IT was mostly attributed to the succulent shrub Portulacaria afra and the canopy trees Euclea undulate, Rhus longispina and Schotia afra. This above-ground biomass translated to biomass C amounts of 158 000 kg/ha at IT, 10 600 kg/ha at DT and 3 200 kg/ha at G. Thus the IT had the highest while G the least and DT moderate plant and soil C sequestration ability. In all, the conversion of IT to DT led to a net loss of 147 000 Kg of biomass C / ha and 12 000kg less organic C / ha of land. Soil carbon dioxide effluxes were however variable between seasons as they were affected by differences in soil properties and seasonal weather patterns. High soil moisture levels (up to 16 percent gravimetric moisture) resulted in reduced soil penetration resistance (1 to 4 Kg/cm2) which raised effluxes at G and DT sites (up to 1.2 μmols m-2 sec-1) in winter, while low moisture (2 percent) resulted in hard dry soil (14 Kgm-2 penetration resistance) with suppressed CO2 effluxes in spring (0.2 μmols m-2 sec-1) especially in DT and G soils. Rising temperature generally caused accelerated gas emissions but only when moisture was not limiting (as was the case in IT). Thus the high summer temperatures (up to 40oC) gave lower effluxes especially in DT and G (< 1 μm-2sec-1) due to limited moisture supply (< 10 percent); while the Autumn period that had very high temperature (up to 48 oC) and good moisture (up to 16 percent) saw accelerated soil CO2 emissions (averaging 2 μmols m-2 sec-1) from all cover types. The high biomass and litter fall at IT served as ready substrate for soil respiration as long as moisture was not limiting and temperatures were favourable, while reduced cover at DT resulted in poor moisture conservation and creation of hard dry soils in spring and summer with reduced respiration. It was concluded that the DT had high CO2 effluxes in winter and reduced emissions in summer; while the opposite was true for the IT. All the cover types had minimal CO2 effluxes in spring and accelerated emissions in autumn. The grassland on the other hand was a fairly moderate source or sink of CO2 in most seasons compared with the other two covers. It was observed that an environment of good moisture and low-moderate temperatures (such as that in the winter) minimises effluxes while maintaining good plant productivity. It was concluded that thicket vegetation is a good sink of carbon that should be preserved in its natural condition to optimize its carbon sequestration potential. All three land covers served as sources or sinks of CO2 depending on soil and seasonal conditions. Thus high moisture and low penetration resistance generally increased effluxes of thicket ecosystems. The effect of increasing temperature on effluxes was only significant when moisture was not limiting. Conditions of good moisture and low-moderate temperatures gave reasonable amounts of effluxes while maintaining good plant productivity. Though the dry soil conditions significantly reduced effluxes in all land covers; they were not desirable since they decreased plant productivity and ultimately its C sequestration potential. Moreover, prolonged dry conditions only serve to exacerbate recovery of thicket plants as they increase mortality of canopy species in degraded and transformed areas in comparison with intact thicket.

Afforestation projects in China have substantially contributed to national CO2 sequestration and play an important role in international climate change mitigation. However, these nation-wide afforestation projects are usually funded by the national government, with very large and unsustainable investments. It is important to find alternative sources of funding to finance afforestation, and convince poor farmers to become involved in afforestation projects. Carbon-subsidized afforestation could be the solution. The current study aims to find i) whether farmers need additional subsidies to reforest their marginal farmland; if so, ii) whether the value of carbon sequestration of afforestation can offset farmers' net costs. To do this, first I determine the amount of carbon sequestration though afforestation. Second, I assess the value of carbon sequestration, the costs and benefits of afforestation projects, and the costs and benefits of crop production. Third, I investigate the optimal rotation period of the plantations considering a joint production of timber and carbon, for different species. Results show that total carbon sequestration through tree biomass and soil carbon following afforestation differs among tree species and stand age as well as across regions. Economic trees sequester less carbon than ecological trees and bamboo. Among economic trees, nut trees with an inedible hard shell sequester more carbon than fruit trees. The regional context significantly influences the carbon sequestration potential, with more carbon sequestered in southern and eastern regions than in northern regions. Bamboo also shows a remarkable carbon sequestration potential, which is even greater than Chinese fir and Poplar in northern regions. Although afforestation programs have huge potential to store carbon, the voluntary acceptance by landowners crucially depends on their economic outcome. I found that usually carbon credits can compensate for the opportunity costs of alternative land uses, except i) when highly profitable croplands are afforested, in which case carbon credits are not sufficient, and ii) when croplands that generates low incomes are afforested, in which case carbon credits are not needed. Fruit trees are the most cost-effective option for afforestation. Bamboo afforestation is economically attractive if carbon revenues is included. The minimum price of carbon credit decreases with increasing project duration because more carbon is stored when time increases. This does not hold for fast-growing trees like Eucalyptus, for which the minimum price increases with extended project duration. Given the temporal variations of joint production of timber and carbon sequestration, the carbon accounting regimes (tCER, temporary Certified Emission Reductions and lCER, long-term Certified Emission Reductions) have a significant impact on the optimal rotation as well as on the revenue. Forest managers have an incentive to use tCER accounting to finance slow-growing plantations, and lCER for fast-growing ones. I perform a sensitivity analysis detects the changes of rotation period with different carbon prices and discount rates. While the optimal decision for slow-growing species (e.g. Chinese fir) is highly sensitive to changes in both variables under tCER accounting, the results concerning fast-growing species (e.g. Eucalyptus) are most sensitive under the lCER accounting regime. In contrast, carbon revenues have a minimal impact on the optimal rotation of Poplar plantations, no matter which regime is applied. I conclude that carbon-subsidized afforestation is a feasible way to offset the opportunity costs of retired farmland and support the livelihood of farmers. The findings can contribute to the efficient and sustainable management of forestry projects using carbon sequestration, while the methodology can also be applied to other regions in the world.

Since the industrial revolution, the atmospheric CO2 concentration has steadily increased due to the combustion of fossil fuels, reaching 410 ppm. According to the 2018 IPCC report, it was recognized that the anthropogenic greenhouse gas emissions caused by human activities are major drivers for global warming of 1.0 oC above the pre-industrial level. Due to the unprecedented scale of human driven CO2 emission and its environmental impact, the mitigation of climate change requires a wide range of multifaceted solutions. Thus, enormous global efforts have been placed on the development of Carbon Capture, Utilization, and Storage (CCUS) to mitigate CO2 emissions in the immediate future. Most recent reports by the U.S. National Academies and the Mission Innovation presented that ex-situ carbon mineralization is a CO2 utilization technology with a great carbon storage potential and a large market size. Also, fixing CO2 into a solid matrix of carbonate minerals is one of the most permanent methods for carbon storage. Although the ex-situ carbon mineralization presents many advantages and great potential as CCUS technology, its commercialization has been limited due to the mammoth scale of the process, slow reaction kinetic between CO2 and silicate minerals, and high energy and operating cost. In order to minimize energy and chemical (acid and base) consumption of this technology, recent researches have been focused on a two-step carbon mineralization via Pco2 swing using highly reactive heat-treated serpentine mineral. However, the elemental (Mg and Si) extractions from the complex silicate structures of heat-treated serpentine are still poorly understood and a more fundamental understanding of the Pco2 swing process is required to develop a commercial-scale plant. Thus, the objectives of this study are directed toward addressing these technical challenges. The effect of operating conditions, such as temperature, slurry density, and CO2 partial pressure, on the dissolution of heat-treated serpentine and subsequent Mg-carbonate precipitation behaviors, were studied to provide a fundamental understanding of the Pco2 swing carbon mineralization process of highly reactive silicate materials. The dissolution experiments with a wide range of temperature and slurry densities provided valuable insights into the formation of the Si-rich passivation layer and its role in the mass transfer limitation during mineral dissolution. The heat-treated serpentine dissolution behaviors with chemical additives (ligand) were also investigated to overcome the effect of the Si-rich passivation layer on Mg extraction kinetics. What is more, a unique internal grinding system was proposed and integrated with the Pco2 swing process to physically remove the Si-rich passivation layer. The diffusion-limited slow elemental (Mg and Si) extraction from the heat-treated serpentine silicate structures was significantly enhanced in the internal grinding system. A stress intensity, which is proportional to the energy transferred from grinding media to the heat-treated serpentine particles during a stress event, was used to describe the effect of the reaction parameters on the extent of the physical activation and the enhancements in mineral dissolution. For the fundamental understanding of the complex dissolution behaviors of heat-treated serpentine, the changes in the silicate structures (Q0 – Q4) of heat-treated Mg-bearing mineral (serpentine) exposed to a CO2-water system (carbonic acid) was investigated using 29Si MAS NMR and XRPD. The identified silicate structures were employed to provide insight into how Mg and Si are liberated from the different silicate structures during the dissolution process. Thermodynamic and kinetic modeling was performed to understand the Mg-carbonate precipitation behaviors in the Pco2 swing process. The effects of carbonic anhydrase, seed particles, and ligand (citrate) on precipitation behaviors were studied to improve the precipitation kinetics. This approach will bring a great paradigm shift in the energy and environmental field since the less energy-intensive and low-cost ex-situ carbon mineralization process via Pco2 swing will be able to allow long-term and sustainable carbon utilization.

Owing to the increased anthropogenic CO₂ emissions over the last several decades, there have been tremendous global efforts in the deployment of renewable energy technologies. However, due to intermittency issues of renewable energy generation and a current lack of reliable long-term energy storage solutions, the development of innovative electrolytes for sustainable energy storage and chemical reactions is an emerging research area. In particular, materials that can host multiple reactions and separations, such as the integrated capture and conversion of CO₂, are highly desired. The direct coupling of renewable energy generation with electrochemical CO₂ conversion to chemicals and fuels is one of the transformative pathways that can aid the global transition to carbon-neutrality, depending on the source of CO₂. However, the current solubility of CO₂ in aqueous electrolytes is quite low (34 mM), thus limiting overall reaction performance. Liquid-like Nanoscale Organic Hybrid Materials (NOHMs) consist of a polymer tethered to a nanoparticle surface and possess a number of favorable properties which are highly desirable in electrochemical applications, including negligible vapor pressure, chemical tunability, oxidative thermal stability and high conductivity. To date, NOHMs have been successfully demonstrated for use as water-lean CO₂ capture solvents, as the polymer canopy can be tuned to capture CO₂ under various sets of operating conditions. Thus, in this dissertation, we have explored the thermal, transport and structural properties of NOHMs in their application as electrolytes enabling the integrated capture and conversion of CO₂. Liquid-like NOHMs functionalized with an ionic bond have been shown to display greatly enhanced oxidative thermal stability compared to the untethered polymer. However, our previous studies were limited in terms of reaction conditions and the detailed mechanisms of the oxidative thermal degradation were not reported. In this study, a kinetic thermal degradation analysis was performed on NOHM-I-HPE and the neat polymer, Jeffamine M2070 (HPE), in both non-oxidative and oxidative conditions. NOHM-I-HPE displayed similar thermal stability to the untethered polymer in a nitrogen environment, but interestingly, the thermal stability of the ionically tethered polymer was significantly enhanced in the presence of air. This observed enhancement of oxidative thermal stability is attributed to the orders of magnitude larger viscosity of the liquid-like NOHMs compared to untethered polymer and the bond stabilization of the ionically tethered polymer in the NOHMs canopy. This study illustrated that NOHMs can serve as functional materials for sustainable energy storage applications because of their excellent oxidative thermal stability, when compared to the untethered polymer. Though NOHMs composed of an ionic bond have demonstrated a high conductivity and an enhanced oxidative thermal stability, their practical application in the neat state is limited by an inherently high viscosity. Thus, when incorporating NOHMs in electrolytes for CO₂ capture and conversion applications, it will be necessary to mix them with a secondary fluid. In this study, a series of binary mixtures of NOHM-I-HPE with five different secondary fluids – water, chloroform, toluene, acetonitrile, and ethyl acetate – were prepared to reduce the fluid viscosity and investigate the effects of secondary fluid properties (i.e., hydrogen bonding ability, polarity, and molar volume) on their transport behaviors including viscosity and diffusivity. Our results revealed that the molecular ratio of secondary fluid to the ether groups of Jeffamine M2070 (λSF) was able to describe the effect that secondary fluid has on transport properties. Our findings also suggest that in solution, the Jeffamine M2070 molecules exist in different nano-scale environments, where some are more strongly associated with the nanoparticle surface than others, and the conformation of the polymer canopy was dependent on the secondary fluid. This understanding of the polymer conformation in NOHMs can allow for the better design of an electrolyte capable of capturing and releasing small gaseous or ionic species. To further investigate the effect of the bond type on the thermal stability as well as the structural and transport properties of the tethered HPE, NOHMs were synthesized by tethering HPE to SiO₂ nanocores via ionic (NOHM-I-HPE) and covalent (NOHM-C-HPE) bonding at two grafting densities. In the neat state, NOHM-C-HPE displayed the highest thermal stability in a nitrogen atmosphere, while NOHM-I-HPE was the most thermally stable under oxidative conditions. Small-angle neutron scattering (SANS) revealed the presence of multiple types of Jeffamine M2070 (HPE) polymers in aqueous solutions of NOHM-I-HPE (i.e., tethered, interacting and free), whereas only tethered HPE chains were observed in NOHM-C-HPE systems. Moreover, the SANS profiles identified clustering of NOHM-C-HPE in dilute aqueous solutions, but not in the corresponding NOHM-I-HPE samples, suggesting that the different types of HPE chains in solutions of NOHM-I-HPE may be crucial to the uniform NOHMs dispersion. Additionally, our investigation of the viscosity and conductivity of different NOHM-based electrolytes revealed that in response to ionic stimulus, the covalently tethered HPE remained fixed at the nanoparticle surface, whereas there was a partial disassociation of HPE chains from the nanoparticle in NOHM-I-HPE. Overall, the results of this study highlight that NOHMs are highly tunable materials whose properties can be strategically altered by changing the bond type linking the polymer to the nanoparticle, as well as grafting density. Finally, two types of aqueous NOHM-based electrolytes were prepared to study the effect of CO₂ Though NOHMs composed of an ionic binding energy (i.e., chemisorption vs. physisorption) on the CO₂ reduction reaction (CO₂RR) over a silver nanoparticle catalyst for the production of syngas, a mixture of H₂ and CO, at various ratios. Poly(ethylenimine) (PEI) and Jeffamine M2070 (HPE) were ionically tethered to SiO₂ nanoparticles to form the amine-containing NOHM-I-PEI and ether containing NOHM-I-HPE, respectively. At less negative applied potentials, PEI and NOHM-I-PEI based electrolytes produced CO at higher rates than 0.1 molal. KHCO₃ due to their enhanced conductivity, while at more negative applied potentials, H₂ production was significantly favored because of the electrochemical inactivity of carbamates and catalyst-electrolyte interactions affecting the selectivity of CO₂RR. Conversely, due to their lower ionic conductivity, HPE and NOHM-I-HPE electrolytes displayed poor CO₂RR performance at less negative applied potentials. At more negative applied potentials, their performance approached that of 0.1 molal. KHCO₃, highlighting how the polymer functional groups of NOHMs are critical to the tunable production of syngas. The results of this study illustrate that more conductive polymer canopies with intermediate binding energies for CO₂ should be explored to improve the performance of NOHM-mediated CO₂ reduction. Altogether, the results of this dissertation demonstrate the ability of NOHM-based electrolytes to be used for systems enabling the integrated capture and electrochemical conversion of CO₂. The polymer grafting density, polymer canopy functionalities, bond type linking the polymer to the nanoparticle, secondary fluid selection and ionic stimulus were all found to play an important role in determining the thermal stability of NOHMs and/or the structural and transport properties of the corresponding NOHM-based fluids/electrolytes, thus highlighting the tunable nature of this class of materials. Additionally, the findings from this dissertation can be applicable to a wide range of energy and environmental applications that require the design and development of novel electrolytes.