<p dir="ltr">Globally, soils hold more carbon than both the atmosphere and aboveground terrestrial biosphere combined. Changes in land use and land cover have the potential to alter soil carbon cycling throughout the soil profile, from the surface to meters deep, yet most studies focus only on the near surface impact (< 25 cm deep). This research bias toward shallow soil carbon cycling has ramifications for understanding the full impacts of agricultural and restoration management practices on soil organic and inorganic carbon dynamics. The primary objective of my thesis research is to evaluate the factors controlling the impact of deep-rooting perennial grass on soil carbon cycling during prairie restoration of soil following long term, row crop agriculture. Paired soil pits were established to compare the effects of restoration on soil C dynamics in a corn-soy cropping system (minimal tillage) and restored prairie sites in Nebraska and Illinois. At each site, soil organic carbon (SOC) and inorganic carbon (SIC) content, stock, and stable carbon isotope analysis were preformed to ~2 m depth to assess long term integrated C dynamics. Estimating the contribution of prairie carbon inputs to the SOC in the soil profile was examined using stable carbon isotopic signatures in the SOC in relation to the above ground vegetation changes in C₃ and C₄ photosynthetic pathway plant community composition. Comparative analysis of edaphic properties and soil carbon suggests that deep loess deposits in Nebraska permit enhanced water infiltration and SOC deposition to depths of ~100 cm in 60 years of prairie restoration. In Illinois, poorly drained, clay/lime rich soils on glacial till and a younger restored prairie age (15 years) restricted the influence of prairie restoration to the upper 30 cm. Comparing the δ¹³C values of SOC and SIC in each system demonstrated that SIC at each site is likely of lithogenic origin. This work indicates that the magnitude of influence of restoration management is dependent on edaphic properties inherited from geological and geomorphological controls. Future work should quantify root structures and redox properties to better understand the influence of rooting depth on soil carbon concentrations. Fast-cycling C dynamics can be assessed using continuous, in-situ CO₂ and O₂ soil gas concentration changes. The secondary objective of my thesis was to determine if manual, low temporal resolution gas sampling and analysis are a low cost and effective means of measuring soil O₂ and CO₂, by comparing it with data from in-situ continuous (hourly) sensors. Manual analysis of soil CO₂ and O₂ from field replicates of buried gas collection cups resulted in measurement differences from the continuous sensors. Measuring CO2 concentration with manual methods often resulted in higher concentrations than hourly, continuous measurements across all sites. Additionally, O₂ concentrations measured by manual methods were higher than hourly values in the restored prairie and less in agricultural sites. A variety of spatial variability, pressure perturbations, calibration offsets, and system leakage influences on both analysis methods could cause the discrepancy.</p>

Master of Science / Department of Chemical Engineering / Larry E. Erickson / The impact of human activities on the atmosphere and the accompanying risks of long-term global climate change are by now familiar topics to many people. Although most of the increase in greenhouse gas (GHG) concentrations is due to carbon dioxide (CO2) emissions from fossil fuels, globally about one-third of the total human-induced warming effect due to GHGs comes from agriculture and land-use. This report provides a brief review of greenhouse effects and impacts on climate, human health and environment. The sources of emissions of greenhouse gases due to human activities, both current estimates and future projections, have been included. The report further discusses possible options for mitigation of greenhouse gases. The report also discusses the role agriculture can play towards mitigation of greenhouse gases as many agricultural processes such as anaerobic digestion, manure gasification; carbon sequestration etc. can help reduce or offset greenhouse gas emissions. Capture and sequestration of CO2 released as a result of burning fossil fuel in power plants, energy and other industries is gaining widespread interest as a potential method of controlling greenhouse gas emissions. Various technologies such as amine (MEA)-based CO2 absorption system for post-combustion flue gas applications have been developed, and can be integrated with existing plant operations. Removal of SO2 by using amine-based carbon capture system offers additional benefit. Efforts are underway to develop a broader suite of carbon capture and sequestration technologies for more comprehensive assessments in the context of multi-pollutant environmental management. Geologic formations and/ or possibly oceans can be used as sinks to store recovered CO2. In oil and gas exploration industry CO2 may be injected in producing or abandoned reservoirs which will not only help in maintaining the reservoir pressure (which improves overall field exploitation) but in some cases even leads to enhanced oil recovery.

Inland waters receive substantial amounts of organic carbon from adjacent watersheds. Only about half of the carbon exported from inland waters reaches the oceans, while the remainder is lost en route. This thesis identifies flocculation as an important and significant fate of carbon in the boreal landscape. Flocculation reallocates organic carbon from the dissolved state into particles which are prone to settle. Thus, flocculation relocates organic carbon from the water column to the sediment. The dissolved organic carbon (DOC), mainly originating from terrestrial sources, in a set of Swedish lakes was found to determine the extent of sedimentation of particulate organic carbon. A major fraction of the settling particles were of allochthonous origin. This implies that allochthonous DOC was the precursor of the settling matter in these lakes. The gross sedimentation was of the same magnitude as the evasion of carbon dioxide to the atmosphere. Sunlight, especially in the photosynthetically active region, stimulated flocculation of DOC. The effect of light appeared to involve a direct photochemical reaction. Iron was involved in the flocculation but it could not be unravelled whether the iron catalyzes the flocculation or just co-precipitates with the settling matter. Microbial activity was identified as the main regulator of the flocculation rates. Accordingly, alteration of temperature, oxygen concentration and pH did not affect flocculation only indirectly, via their effects on microbial metabolism. A comparison of fluorescence characteristics of organic matter collected in sediment trap and in the sediment surface layer revealed that autochthonous organic carbon was preferentially lost in the sediments while allochthonous matter increased. The recalcitrant nature of the flocculated matter could favour sequestration of this matter in the lake sediment. Hence, the lakes will act as sinks of organic carbon due to a slower mineralization of the flocculated matter in the sediments.

L’utilisation des microorganismes marins ou terrestres pour la séquestration à long terme du CO2 est une des solutions envisagées pour diminuer la teneur en CO2 dans l'atmosphère. Le travail de cette thèse se concentre sur les microorganismes calcifiants, et notamment les cyanobactéries, qui peuvent fixer du CO2 sous forme de biomasse et carbonate de calcium. Ce dernier, insoluble dans l’eau, précipite et peut donc constituer un puits à long terme. La compréhension des mécanismes de calcification induits par les cyanobactéries et la possibilité de contrôler ces processus sont nécessaires pour développer une technologie de séquestration du CO2. Cette biotechnologie pourrait constituer une alternative à la technologie de capture et stockage géologique du CO2. Synechococcus PCC8806 une souche marine de cyanobactérie purifiée à l'Institut Pasteur de Paris est utilisée comme organisme au cours du travail expérimental réalisé dans le cadre de cette thèse. Le premier résultat important de cette thèse est le développement d'une stratégie analytique ayant permis d'accéder à un bilan de masse carbone et calcium au cours d'une culture de cyanobactérie sur hydrogénocarbonate. La mise en œuvre de cette stratégie au cours de différents essais réalisés dans le cadre de ce travail a permis par ailleurs de quantifier avec précision la production de carbone organique (biomasse) et de carbone inorganique (CaCO3) en fonction du calcium et du carbone inorganique présent dans les milieux de culture. Nous avons ensuite étudié la précipitation de la calcite au cours de la croissance de Synechococcus PCC8806 en présence de calcium. Pour cela les conditions de culture ont été variées de telle sorte que la survenue des évènements de précipitations a pu être comprise ainsi que l'influence de sites de nucléation mis en évidence. Le grossissement des cristaux a également été étudié attentivement par microscopie électronique à balayage. Une autre partie de ce travail a permis d'identifier la source de carbone inorganique utilisée par Synechococcus PCC8806 pour la photosynthèse. Cela a été l'occasion de réécrire les équations liées aux transferts entre le CO2 atmosphérique et le système carbonaté, ainsi que les équations de photosynthèse en fonction des conditions de disponibilité des deux sources de carbone inorganique (CO2 et hydrogénocarbonate). De plus ont pu être mis en évidence, les effets des phases diurne et nocturne de la croissance de cyanobactéries sur les équilibres du système carbonaté et le pH. Ce travail a également permis de déterminer les vitesses de croissance des cyanobactéries et donc de calculer des rendements de croissance par unité de surface. Cela permettra à terme d'optimiser la production de biomasse et de calcite dans un procédé industriel / The use of marine or terrestrial microorganisms for long-term sequestration of CO2 is a possible solution to reduce the CO2 content in atmosphere. This thesis work focuses on calcifying organisms, in particular the cyanobacteria, which can fix CO2 as biomass and calcium carbonate. The latter is insoluble in water; precipitates may therefore constitute a long term sink. Understanding of the calcification mechanisms induced by cyanobacteria and the possibility of controlling these processes are necessary to develop a technology for CO2 sequestration. This biotechnology could be an alternative technology to CO2 capture and geological storage. Synechococcus strain PCC8806, marine cyanobacteria purified by the Institute Pasteur de Paris is used during the experimental work in this thesis. The first important result of this work is to develop an analytical strategy that allowed access to a mass balance of carbon and calcium in a cyanobacteria culture on hydrogencarbonate. The implementation of this strategy in various tests of this work has also allowed to accurately quantify the production of organic carbon (biomass) and inorganic carbon (CaCO3) according to the calcium and Ci introduced (hydrogencarbonate) in the medium. We then studied the calcite precipitation during growth of Synechococcus PCC8806 in the presence of calcium. For that, culture conditions were varied in order to understand the occurrence of precipitation events and the influence of nucleation sites. The development of crystals has also been carefully studied by scanning electron microscopy. Another part of this work has identified the inorganic carbon source used by Synechococcus PCC8806 for photosynthesis. This was an opportunity to rewrite the equations related to transfers between atmospheric CO2 and the carbonate medium, as well as the equations of photosynthesis depending on the conditions of availability of two sources of inorganic carbon (CO2 and hydrogencarbonate). In addition, we have revealed the effects of diurnal and nocturnal phases of the growth of cyanobacteria on the carbonate system balance and pH. This work also allowed estimating the cyanobacteria growth rates and thus calculating growth yields per unit area. This will ultimately optimize biomass and calcite production in an industrial process

Nitrogen (N) fertilization due to atmospheric deposition (NDEP ) may explain some of the net carbon (C) sink (0.6-0.7 Pg y-1) in temperate forests, but estimates of the additional C uptake due to atmospheric N additions (∆C/∆N) can vary by over an order of magnitude (5 to 200 ∆C/∆N). High estimates from several recent studies [e.g. Magnani (2007), Nature 447 848-850], deriving ∆C/∆N from regional correlations between NDEP and measures of C uptake (such as eddy covariance -derived net ecosystem production, or forest inventory data) contradict estimates from other studies, particularly those involving 15N tracer applications added as fertilizer to the forest floor. A strong ∆C/∆N effect requires nitrogen to be efficiently acquired by trees and allocated to high C:N, long-lived woody tissues, but these isotope experiments typically report relatively little (~ 20 %) of 15N added is found above-ground, with less than 5 % of the total 15N applied found in wood. Consequently the high correlation-derived ∆C/∆N estimates are often attributed to co-variation with other factors across the range of sites investigated. However, 15N-fertilization treatments often impose considerably higher total N loads than ambient NDEP , while almost all exclusively only apply mineral 15N treatments to the soil, often in a limited number of treatment events over relatively short periods of time. Excessive N deposition loads can induce negative physiological effects and limit the resulting ∆C/∆N observed, and applying treatments to the soil ignores canopy nitrogen uptake, which has been demonstrated in numerous studies. As canopies can directly take up nitrogen, the chronic, (relatively) low levels of ambient NDEP inputs from pollution may be acquired without some of the effects of heavy N loads, with trees obtaining this N before it reaches the soil, allowing canopies to substitute for, or supplement, edaphic N nutrition. The strength of this effect depends on how much N uptake can occur across the canopy under field conditions, and if this extra N supplies growth in woody tissues such as the stem, as well as the canopy. Similarly, such mineral fertilizer isotope trace experiments are also unable to trace N in the decomposing litter and humus layers of the soil, which even under heavy NDEP loading contribute most of the N utilised for forest growth. Recent literature suggests that some organic (early decomposition) forms of N may be taken up by roots. If this litter N is not retained or distributed in the same way as mineral fertilizers, its contribution to plant nutrition and ∆C/∆N may need to be reassessed under nitrogen deposition. We tested some of these assumptions in the nursery and the field. In order to facilitate litter 15N tracing, we conducted an experiment injecting large trees with 15N-NH4NO3 to create 15N-labelled litter, tracing the applied isotope into a full harvest of the canopy. Such labelled litter substitute was used to replace the litter layer in a Sitka Spruce plantation (Picea sitchensis L. (Bong.)), where the fate of this 15N from litter decomposition in the soil system was compared against the fate of 15N in deposition. Similarly, in potted Sitka Spruce saplings, we used combination treatments of 15N-labelled litter, soil-targeted 15N-deposition, and canopy targeted 15N-deposition, investigating 15N return in different age classes of above and below ground biomass. We found that i) 15N recovery in canopies (needles and branches) in our injected trees was almost all of the injected 15N five months after injection, ii) canopy application of NDEP led to 60 % 15N return in above-ground parts of saplings compared to 21 % in soil applications and iii) a litter-derived 15N source was retained 55 % more in topsoil, and 36 % more in roots, than a similar deposition 15N source applied as mineral fertilizer. We discuss the implications of such findings in the context of 15N return in different plant organs and ecosystem pools, seasonal variation in N content, and overall inferences of a forest ∆C/∆N effect. Our results suggest that the total ∆C/∆N effect driven by a high N sequestration from canopy uptake in wood is ~ 114:1, more than double that of 15N tracer experiments but not as high as upper estimates from correlative studies, and that litter-derived organic N is better retained in trees and soils in excess of similar amounts of mineral 15N from deposition. Existing forest 15N-fertilization experiments could under-estimate the overall ∆C/∆N effect of atmospheric N deposition.

Doctor of Philosophy / Department of Agronomy / Charles W. Rice / Increasing atmospheric CO2 concentrations and other greenhouse gases have been linked to global climate change. Soil organic C (SOC) sequestration in both agricultural and native ecosystems is a plausible option to mitigate increasing atmospheric CO2 in the short term. Laboratory and field studies were conducted to (1) understand the influence of soil water content on the temperature response of SOC mineralization (2) investigate burn and nutrient amendment effects on biogeochemical properties of tallgrass prairie and (3) assess perennial and annual plant management practices on biophysical controls on SOC dynamics. The laboratory study was conducted using soils collected from an agricultural field, currently planted to corn (C4 crop), but previously planted to small grain (C3) crops. The changes in cultivated crops resulted in a δ¹³C isotopic signature that was useful in distinguishing older from younger soil derived CO2-C during SOC mineralization. Soils were incubated at 15, 25 and 35 oC, under soil water potentials of -1, -0.03 and -0.01 MPa. Soil water content influenced the effect of temperature on SOC mineralization. The impact of soil water on temperature effect on SOC mineralization was greater under wetter soil conditions. Both young and older SOC were temperature sensitive, but SOC loss depended on the magnitude of temperature change, soil water content and experiment duration. Microbial biomass was reduced with increasing soil water content. The first field experiment investigated burn and nutrient amendment effects on soil OC in a tallgrass prairie ecosystem. The main plots were burned (B) and unburned (UB) tallgrass prairie and split plots were nutrient amendments (N, P or N+P including controls). Vegetation was significantly altered by burning and nutrient amendment. Treatment effects on either TN or SOC were depth-specific with no impact at the cumulative 0-30 cm depth. The P amendment increased microbial biomass at 0-5 cm which was higher in unburned than burned. However, at 5-15 cm depth N amendment increased microbial biomass which was higher in burned than unburned. In conclusion, soil OC in both burned and unburned tallgrass prairie may have a similar trajectory however; the belowground dynamics of the burned and unburned tallgrass prairie are apparently different. Another field experiment assessed SOC dynamics under perennial and annual plant management practices. The main plots were grain sorghum (Sorghum bicolor) planted in no-tillage (NT) or continuous tillage (CT), and replanted native prairie grass, (Andropogon gerardii) (RP). The spit plots were phosphorus (+P) and control without P (-P). The P amendment was used to repress arbuscular mycorrhizal fungi (AMF), known to influence soil aggregation. The macroaggregate >250 µm, SOC and TN were higher in RP and NT than CT. The relative abundances of AMF and saprophytic fungi were greater with less soil disturbance in RP and NT than in CT. Therefore, less soil disturbance in RP and NT increased AMF and fungal biomasses. The higher relative abundances of AMF and fungi with less soil disturbance increased macroaggregate formation in RP and NT, which resulted in higher SOC sequestration in RP and NT than CT.

Seagrass meadows may play a substantial role in climate change mitigation as they are capable to sequester and store substantial amounts of anthropogenic carbon in plant biomass and, more importantly, in their underlying sediments. In this PhD thesis, the carbon-burial potential was assessed by quantifying the amount of organic carbon stored in different seagrass meadows, each dominated by one of the four major seagrass species in the Western Indian Ocean region. Impacts of anthropogenic disturbances on biomass carbon allocation, greenhouse gas emission (methane and nitrous oxide) and production of sulphide were investigated in Chwaka Bay, Zanzibar. The findings showed that east African seagrass meadows generally have high carbon sink capacity. The storage of sedimentary organic carbon, however, varied among seagrass habitats and across sites, and was up to five-fold higher in seagrass sediment to those of nearby unvegetated sediments. Seagrass meadows in eutrophicated sites had higher sedimentary organic carbon content, and substantially higher emission rates of nitrous oxides and methane, compared to more pristine meadows. Disturbances in terms of shading and simulated grazing of seagrass affected several processes, with major decreases in seagrass primary productivity, net community production and biomass carbon, in turn influencing seagrass carbon sequestration as well as stimulating anaerobic microbial processes. In addition, production of sulphide in the sediment and methane emissions from the sediment surface increased significantly when disturbed. At present, seagrass meadows in the Western Indian Ocean have high carbon sink capacity. This important ecosystem service is, however, highly threatened due to regional anthropogenic pressure, which may change the role of blue carbon rich habitats, such as seagrass meadows, from being a sink to a source of greenhouse gases. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Manuscript. Paper 2: Manuscript. Paper 4: Manuscript. Paper 5: Manuscript.</p>

Proveniente do processo de pirólise, o biochar é constituído por elevado teor de carbono, em estruturas que são responsáveis pela elevada resistência à degradação. O material vem sendo objeto de estudo por seus diversos usos e benefícios que oferece ao ambiente. Quando aplicado ao solo traz melhorias relacionadas às propriedades químicas, físicas e microbiológicas do mesmo, além de ser ferramenta para o sequestro de carbono, alternativa para disposição de resíduos orgânicos com concomitante produção de energia. Entretanto, as propriedades químicas e físicas dos biochars variam grandemente devido à diversidade de matérias-primas e das condições de produção. O presente estudo visou avaliar a variação das propriedades físicas, químicas e morfológicas do biochar e a influência da matéria-prima e da temperatura de pirólise na caracterização final do produto. Para tanto, foram produzidos biochars oriundos da combinaçao de quatro temperaturas (350, 450, 550 e 650 °C) e de quatro matérias-primas (palha de cana-de-açúcar, casca de arroz, dejeto de galinha e serragem). Em todos os produtos e materiais de origem foram feitas avaliações de pH, condutividade elétrica (C.E.), capacidade de troca catiônica (CTC), teor de carbono (C), nitrogênio (N), hidrogênio (H), material volátil e cinzas, teor de nutrientes, além de avaliação de espectroscopia através de Infravermelho por Transformada de Fourier (FTIR), análise de morfologia por Microscopia Eletrônica de Varredura, análise de termogravimetria e teores de lignina celulose e hemicelulose. Constatou-se variação de algumas proprieades químicas como os teores de C, H, O, materiais voláteis, cinzas, carbono fixo, índice pH, condutividade elétrica e capacidade de troca catiônica com maior influência da temperatura de pirólise. O teor inicial de macro e micronutrientes presentes nas matérias-primas apresentou maior influência na variação das concentrações desses nutrientes nos biochars. De forma geral observou-se aumento da estabilidade química nos diferentes biochars com a elevação da temperatura de pirólise. A recalcitrância dos biochars confere-lhes persitência no solo e é confirmada pelo aumento dos teores de C e diminuição da emissão de CO2 nos tratamentos com adição desses materiais em comparação com adição de suas respectivas matérias-primas. Ademais, a contribuição dos biochars para elevação no pH do solo é de fundamental importância para sua adoção na agricultura sob o ponto de vista de fertilidade do solo. / A product of pyrolysis, biochar is a carbon rich material and its structure is responsible for the high resistance to degradation. Biochar is an interesting object of study due to its diverse applications and amendments to the environment. When applied to the soil, it is able to enhance soil physical, chemical and microbiological properties. It is also pointed as an instrument to sequester carbon and an alternative disposal for organic residues as well as energy source. However, the resultant properties of biochar vary greatly considering the diverse options of feedstocks combined with the contrasting production conditions used to obtain the final product. The present study aimed the evaluation of the different chemical and physical properties within a range of diverse biochars, and the assessment of feedstock or pyrolysis temperature mediated changes. The biochars produced combined pyrolysis temperatures (350, 450, 550 and 650 °C) with four feedstocks (sugar cane straw, rice husk, poultry manure and sawdust). In order to assess biochar properties and the temperature or feedstock mediated changes, several analysis were performed in the feedstock and biochars produced. The analysis included pH, cation exchange capacity, carbon, nitrogen and hydrogen content, proximate analysis, nutrient content, as well as spectroscopy performances such as Fourier Transformed Infrared (FTIR), morphological assessment through Scanning Electron Microscopy (SEM), termogravimetric analysis and lignin, cellulose and hemicellulose contents. The results suggests that temperature influenced greatly some of the chemical properties assessed, such as the contents of C, H, O, volatile matter, ash, fixed C, pH, electrical conductivity, cation exchange capacity. Feedstocks initial macro and micronutrient contents exhibited more influence in the variation of these elements in the biochars. In general, there was an increase in chemical stability in the different biochars with increasing pyrolysis temperature. The high recalcitrance found in biochars enable them to persist within the soil, which was confirmed by the increased levels of C content and decreased CO2 emissions when biochars addition was compared with their feedstocks addition to soils. Moreover, the contribution of biochar in increasing soil pH is very important from a soil fertility standpoint.

With the atmospheric concentration of carbon dioxide steadily increasing and little sign of a reduction in fossil fuel demand worldwide, there is a well-established need for an alternative strategy for dealing with carbon emissions from energy production. One possible solution is the accelerated weathering of ultramafic rocks. Accelerated weathering is an environmentally benign route to a thermodynamically and kinetically stable form of carbon. The chemistry is based on naturally occurring reactions and the raw materials are abundant across the earth's surface. However, the reactions are relatively slow, and achieving reaction rates sufficient to match the carbon dioxide production rate at an energy conversion facility is challenging. This work addresses a number of the challenges facing the integration of accelerated weathering with energy conversion, and presents one view of how the integration could be achieved. This work begins by developing a suite of tools necessary for investigating the dissolution and precipitation of minerals. Chapter 2 starts with a description of the minerals that will be evaluated, and then goes on to develop the techniques that will be used. The first is a differential bed reactor, which is used for measuring the dissolution rates of minerals under tightly controlled conditions. Next a bubble column reactor is developed for the investigating the adsorption of carbon dioxide and the precipitation of mineral carbonates in a single vessel. These techniques, together with a batch reactor for studying direct carbonation reactions, constitute a comprehensive set of tools for the investigation of accelerated mineral weathering. With the necessary techniques developed and proven, Chapter 3 addresses the first challenge faced by accelerated mineral weathering; the dissolution rate of magnesium from a silicate mineral. While the dissolution of this mineral is thermodynamically favorable, the kinetics are prohibitively slow. It is thought that this is because silica from the mineral tends to accumulate on the particle surface creating a passivation layer, which limits the reaction rate of the mineral. In this work, the effects of a combination of chemical chelating agents, catechol and oxalate, are evaluated for their ability to circumvent this passivation layer. The results indicate that catechol and oxalate modify the passivation layer as it forms, both accelerating the dissolution rate of the mineral and maintaining pore volume, leading to greater dissolution rates. This pore modification process is proposed as the primary mechanism by which catechol affects the passivation layer. The combination of catechol and oxalate under acidic conditions is also shown be effective when the ambient solution approaches the saturation point of silica. Finally, the chelating does not impede the precipitation of carbonate products, a critical hurdle for a carbon storage process. The chelating agent work is extended in Chapter 4, with a sensitivity study that evaluates the response of the dissolution rate to changes in both pH and the concentration of the chelating agents. Oxalate and pH are found to exhibit a strong influence on the mineral dissolution rate, while the effect of catechol is more apparent after significant dissolution has taken place. These observations are in agreement with the model of passivation layer modification proposed. In addition, some alternatives to the chelating agent catechol are evaluated. It is found that when used in combination with oxalate, these alternatives appeared equivalent to catechol, but alone they had only a minor effect. Catechol was also noted to have a significant effect on the dissolution rate of iron from the silicate mineral, and a mechanism for this effect was proposed. The direct adsorption of carbon dioxide and precipitation of solid carbonates in a single reaction step presents another challenge for accelerated mineral carbonation. In general, the magnesium carbonates formed at ambient pressure and moderate temperatures tend to be hydrated, and at times contain unused hydroxides, leading to inefficiencies in both transport and storage. It is shown in Chapter 5 that by seeding reaction vessels with the anhydrous form of magnesium carbonate, it is possible to grow this desired phase with minimal formation of the metastable hydrated phases. The formation of this phase is primarily limited by the precipitation rate, but in some situations, carbon dioxide hydration kinetics and magnesium hydroxide precipitation kinetics also play a role. In Chapter 6, these developments in both magnesium silicate dissolution and carbonate precipitation are combined into a proposed technology for the direct capture and storage of carbon dioxide. This application of accelerated mineral weathering is shown to significantly reduce the carbon emissions of an energy conversion technology through life cycle assessment. This novel approach to the mitigation of carbon emissions presents a compelling argument for the continued development of accelerated mineral weathering as a combined carbon capture and storage technology.

Rising concentration of CO2 in the atmosphere is attributed to increasing consumption of fossil fuels. One of the most effective mechanisms to store CO2 captured from power plants is via geological injection of CO2 into formations that contain calcium and magnesium silicate and alumino-silicate minerals and rocks. The mechanism that ensures permanent storage of CO2 within rocks is mineral carbonation. When CO2 is injected into mineral or rock formations rich in calcium or magnesium silicates, they react with CO2 to form calcium or magnesium carbonates, which is also known as carbon mineralization. Calcium and magnesium carbonates are stable and insoluble in water. However, the kinetics of in-situ mineral carbonation involve CO2 hydration, mineral dissolution and formation of carbonates, and the relative rates of these phenomena when coupled, are not very well understood. In this study, the coupled interactions of CO2-reaction fluid-minerals were investigated to determine the optimal conditions for carbon mineralization, and to identify the chemical and morphological changes in the minerals as they react to form carbonates. Carbon mineralization in various minerals and rocks such as olivine ((Mg,Fe)2SiO4)), labradorite ((Ca, Na)(Al, Si)4O8), anorthosite (mixture of anorthite (CaAl2Si2O8), and basalt (rock comprising various minerals) were studied at high temperatures (Tmax = 185 oC) and high partial pressures of CO2 (PCO2, max = 164 atm) which are relevant for in-situ conditions. These minerals and rocks differ considerably in their chemical compositions and reactivity with CO2. A systematic comparison of the effects of reaction time, temperature, partial pressure of CO2, and fluid composition on the conversion of these magnesium and calcium bearing minerals and rocks showed that olivine was the most reactive mineral followed by labradorite, anorthosite, and basalt, respectively. Previous studies at Albany Research Center (Gerdemann et al., 2007; O'Connor et al., 2004) reported that a solution of 1.0 M NaCl + 0.64 M NaHCO3 was effective in achieving high extents of carbonation in olivine, heat-treated serpentine, and wollastonite. However, the independent effects of NaCl and NaHCO3 and their role in mineral carbonation were not sufficiently explained. In this study, the role of varying concentrations of NaCl and NaHCO3 on carbon mineralization of various minerals was elucidated. NaHCO3 buffered the pH and served as a carbon carrier, resulting in higher carbonate conversions. Except in the case of olivine, NaCl had a negligible effect on enhancing mineral carbonation. Unlike NaHCO3, NaCl does not buffer the pH or serve as a carbon carrier, but Cl- may serve as a weak chelating agent can complex with Mg or Ca in the mineral matrix to enhance dissolution. The competing effects of ionic strength and pH swings as the mineral dissolves and carbonation further complicate the role of NaCl on mineral carbonation. Based on the experimental methodologies developed to study carbon mineralization in minerals and rocks at high temperatures and pressures, alternative applications such as the remediation of hazardous alkaline wastes such as asbestos containing materials were identified. Asbestos is composed of chrysotile, a fibrous hydrated magnesium silicate mineral and a form of serpentine known to cause respiratory illnesses. By treating asbestos containing materials with CO2 in the presence of 0.1 M Na-oxalate, dissolution of chrysotile and precipitation of newer phases such as glushinkite (Mg(C2O4)* 2H2O) and magnesite (MgCO3) occurred, which reduced the chrysotile content in asbestos. Based on the methodologies for studying mineral dissolution and carbonation kinetics, and coupled mineral dissolution and carbonation behavior, a scheme for connecting laboratory scale experiments with simulations to estimate the uncertainties associated with carbon mineralization was developed. The effects of temperature, different dissolution rates, and varying levels of surface area changes due to passivation or reactive cracking on the rates of carbon mineralization were simulated using PhreeqC, a computer program developed for geochemical speciation calculations (Parkhurst & Appelo, 1999). Various studies proposed that microfractures and cracks may occur in geologic formations due to the extensive growth of carbonate crystals (Kelemen & Hirth, 2012; Kelemen & Matter, 2008; Matter & Kelemen, 2009; Rudge et al., 2010). Other studies have suggested that the formation of carbonates may plug the pore spaces and limit further reactivity (Hövelmann et al., 2012; King et al., 2010; Xu et al., 2004). The effects of changes in surface area due to the formation of microfractures or passivation due to carbonate growth on the rates of carbon mineralization were also simulated. Overall the results of these studies demonstrate the effect of various parameters on carbon mineralization and how these parameters can be connected to predict CO2 storage in mineral formations. The frameworks to connect laboratory scale experiments with simulations to determine carbon mineralization rates and to assess the risks associated with CO2 injection in reactive formations, can be used to direct future research efforts to predict the fate of injected CO2 with greater accuracy for sensor placement and optimization of CO2 monitoring technologies.