As emissões globais de gases do efeito estufa (GEE) devido a ações do ser humano tem levado a um aumento na temperatura média da superfície terrestre de 0,55oC, e mudanças climáticas como aumento de eventos climáticos extremos, elevação dos níveis dos oceanos, e mudanças nos regimes pluviométricos são alguns exemplos das possíveis implicações deste aquecimento. O carbono orgânico do solo (COS) é o principal reservatório terrestre de C, contendo mais que o dobro do C da atmosfera, portanto, dependendo do manejo os solos podem se transformar em importantes fontes ou drenos de C atmosférico, influenciando significativamente os efeitos do aquecimento global. O objetivo desta pesquisa foi estimar as mudanças nos estoques do COS devido às mudanças no uso da terra e sistemas de manejo nos estados de Rondônia e Mato Grosso entre 1970 e 1985 e 1985 a 2002 utilizando dados específicos da região; e realizar a análise de incerteza destas estimativas mediante o método de Monte Carlo. Para alcançar o objetivo principal, a presente pesquisa foi composta das seguintes etapas: i) cálculo dos estoques do COS sob vegetação nativa (carbono de referência); ii) obtenção dos dados (áreas) das principais categorias de uso da terra nos estados de Rondônia e Mato Grosso para os anos de 1970, 1985 e 2002, a partir da combinação de técnicas de sensoriamento remoto, dados dos censos agropecuários, e informações de especialistas do setor agropecuário; iii) desenvolvimento dos fatores de emissão específicos para os principais sistemas de manejo da região de estudo utilizando um modelo linear misto; iv) e a etapa final que consistiu em combinar as etapas anteriores para se estimar as mudanças nos estoques de COS, e realizar a análise das incertezas associadas. Sucintamente, foram derivados fatores de emissão para as pastagens degradadas (0,91 ± 0,14), típicas em Latossolos (0,99 ± 0,08), típicas nos demais tipos de solos (1,24 ± 0,07), e pastagens melhoradas em Latossolos (1,19 ± 0,07), todos os fatores representam a comparação entre as pastagens manejadas e a vegetação nativa. Nos sistemas agrícolas foi possível derivar fatores de emissão para sistemas de plantio direto (PD) em áreas de Cerrado (1,08 ± 0,06), PD em áreas de floresta Amazônica e Cerradão (1,01 ± 0,17), cultivo convencional (CC) (0,94 ± 0,04) e culturas perenes (0,98 ± 0,14), sendo que o fator para o CC foi comparado aos dados de PD, enquanto que os demais fatores foram obtidos a partir da comparação com os estoques sob vegetações nativas. Quanto às emissões de COS, foi encontrado que usando o método de Monte Carlo com 20000 simulações no período de 1970 a 1985, os solos minerais apresentaram uma perda de C com fluxos anuais de 4,28 e 1,14 Tg C ano-1, para Mato Grosso e Rondônia, respectivamente, e com 95% de intervalo de confiança as incertezas foram de ± 41,5 e 21,9%, respectivamente. No segundo período, as emissões foram de 2,86 e 0,91 Tg C ano-1, com incertezas de ± 40,1 e 33,8%, respectivamente, para Mato Grosso e Rondônia. Quanto às fontes de incerteza, o carbono de referência, a opinião dos especialistas sobre as condições das pastagens e os fatores de emissão para pastagens típicas e degradadas foram às variáveis responsáveis por mais de 90% das incertezas das estimativas das emissões de C do solo. / Global emissions of greenhouse gases (GHG) due to human beings actions have led to an increase in average temperature of the earth of 0,55oC, and climate changes such as increases of the extreme weather events, sea level rise and precipitation changes are some examples of the possible implications of this global warming. Soil organic carbon (SOC) is the largest terrestrial organic carbon pool, containing more than the double of the atmospheric C; therefore, depending on the management the soils can became a source or a sink for the atmospheric C, influencing the effects of global warming. The objective of this research was to estimate the changes in SOC stocks due to the land-use and management systems in the states of Rondônia and Mato Grosso from 1970 to 1985 and from 1985 to 2002 using regional specific data, and perform the uncertainty analysis of these estimates through the Monte Carlo method. To achieve the main objective, this research was composed by the following steps: i) the estimate of the SOC stocks under native vegetation (reference carbon), ii) obtain data (areas) of the main land-use categories in the states of Rondônia and Mato Grosso for the years 1970, 1985 and 2002, from a combination of remote sensing, agricultural census data, and information from experts of the agricultural sector, iii) to derive the emission factors specific to the major management systems in the region of study using a linear-mixed model; iv) the final step was to combine the above steps to estimate the changes in SOC stocks, and carry out the uncertainty analysis associated with them. Briefly, emission factors were derived to the degraded grasslands (0.91 ± 0.14), typical in Oxisols (0.99 ± 0.08), typical in other soil types (1.24 ± 0.07), and improved grasslands in Oxisols (1.19 ± 0.07), all factors represent the comparison between managed pastures and native vegetation. In agricultural systems could be derived emission factors for no tillage (NT) systems in the Cerrado areas (1.08 ± 0.06), NT in Amazon Forest and Cerradão areas (1.01 ± 0.17), conventional tillage (CT) (0.94 ± 0.04), and perennial crops (0.98 ± 0.14). However, the CT factor was obtained from the comparison with NT data, while the other factors were compared to SOC stocks under the native vegetation. Using the Monte Carlo approach with 20000 simulations it was estimated the changes in the SOC stocks and the uncertainties associated to them. In the period from 1970 to 1985, mineral soils had a loss of C with annual fluxes of 4.28 and 1.14 Tg C yr-1, in Mato Grosso and Rondônia, respectively, and with a 95% confidence interval the uncertainties were of ± 41.5 and 21.9% respectively. In the second period, emissions were of 2.86 and 0.91 Tg C yr-1, with uncertainty of ± 40.1 and 33.8%, respectively, in Mato Grosso and Rondônia. In terms of the sources of uncertainty, the reference carbon, the experts opinions about the grasslands, and the emission factors for typical and degraded grassland were the variables responsible for more than 90% of the uncertainties in the SOC emissions estimates.

Mangroves are coastal ecosystems that provide many ecosystem services, for example: (i) carbon sequestration; (ii) mitigation of greenhouse gas emissions; (iii) retention and immobilization of contaminants; (iv) nursery for several marine species; so it is necessary to develop mangrove protection and recovery initiatives, which are among the most impacted and degraded ecosystems in the world. In addition, many ecosystem services are related to pedogenetic soil processes, however, few studies have carried out this approach. Therefore, this study aimed to analyze two mangrove recovery initiatives in different soil contexts, aiming at identifying the restoration of pedogenetic processes and soil quality. Therefore, two mangroves with reforestation areas were analyzed in two compartments of the Brazilian coast: a) one in the state of Ceará (CE) located in the northeast region marked by a source material rich in quartz and semiarid climate; b) another located in the state of Rio de Janeiro (RJ), in the Southeast region, which presents material rich in iron and a humid tropical climate. In both sites, it was possible to observe the reestablishment of pedogenetic processes such as paludization, gleization and sulfidization, which are related to ecosystem services such as carbon sequestration and retention and immobilization of contaminants. Our study also identified the soil quality improvement using the Soil Management Assessment Framework (SMAF) tool, it is emphasized that this approach has never been used in studies involving mangroves. In fact, mangrove revegetation initiatives were able to increase soil quality of parameters such as: bulk density, carbon content, phosphorus content and pH, and the increase in soil quality positively affected the restoration of ecosystem functions such as sequestering carbon. In addition, the SMAF tool proved to be a useful tool for studies of soil quality, however, adjustments should be considered, as well as the number of variables inserted. In general we also identify that the reestablishment of pedogenetic processes may occur in a short period of time and that this approach is fundamental to infer about the capacity of impacted mangroves to develop their ecosystem functions. / Manguezais são ecossistemas costeiros que provisionam múltiplos serviços ecossistêmicos, por exemplo: (i) sequestro de carbono; (ii) mitigação das emissões de gases de efeito estufa; (iii) retenção e imobilização de contaminante; (iv) berçário para diversas espécies marinhas. Assim é necessário desenvolver iniciativas de proteção e recuperação de manguezais, uma vez que estão entre os ecossistemas mais impactados e degradados em todo o mundo. Neste sentido, muitos serviços ecossistêmicos estão relacionados a processos pedogenéticos do solo, no entanto, poucos estudos realizaram essa abordagem. Diante disso, este estudo teve como objetivo analisar duas iniciativas de recuperação de manguezais, em diferentes contextos edáficos, visando identificar o restabelecimento de processos pedogenéticos e a restauração da qualidade do solo. Portanto, foram analisados dois manguezais com áreas de replantio em dois compartimentos da costa brasileira: a) um no estado do Ceará (CE) localizado na região nordeste marcada por um material de origem rico em quartzo e clima semiárido; b) outro localizado no estado do Rio de Janeiro (RJ), região Sudeste, que apresenta material de origem rico em ferro e clima tropical úmido. Em ambos os locais estudados foi possível observar em resposta ao desenvolvimento da vegetação, o restabelecimento de processos pedogenéticos como paludização, gleização e sulfidização que estão relacionados à serviços ecossistêmicos como sequestro de carbono e retenção e imobilização de contaminantes. Nosso estudo também identificou o aumento qualidade do solo utilizando a ferramenta Soil Management Assessment Framework (SMAF), ressalta-se que essa é uma abordagem que nunca foi utilizada em estudos envolvendo manguezais. De fato, as iniciativas de revegetação de manguezais foram capazes aumentar a qualidade do solo a partir de parâmetros como: densidade, conteúdo de carbono, conteúdo de fósforo e pH e o aumento da qualidade do solo afetou positivamente o restabelecimento de funções ecossistêmicas como sequestro de carbono. Além disso, a ferramenta SMAF mostrou-se ser uma ferramenta útil para estudos de qualidade do solo, no entanto ajustes devem ser considerados, assim como o número de variáveis inseridas. Em geral também identificamos que o restabelecimento de processos de pedogenéticos pode ocorrer em curto período de tempo e que essa abordagem é fundamental para inferir sobre a capacidade de manguezais impactados de desenvolver suas funções ecossistêmicas.

Australia’s economy is heavily dependent on coal-based energy and greenhouse gas intensive natural resource extraction and processing industries. As part of an international climate change mitigation effort Australia will have to undergo a national transformation to a low emissions society by mid century. Federal and State Governments in Australia, like their counterparts in other major developed economies, have been persuaded that reliance on fossil fuels in stationary energy industries such as electricity generation and minerals processing will be able to continue with the deployment of a value chain of technologies fitted to these installations for capturing carbon dioxide, transporting it to a disposal site, and then injecting it into subsurface geological formations for permanent storage (carbon capture and storage, or CCS). Understanding the likely effectiveness of CCS for reducing greenhouse gas emissions from stationary energy industries is therefore critical to policy formulation for, and management of, Australia’s emissions mitigation effort and national transformation over the decades ahead. / This thesis aims to offer a clearer understanding of the practicalities, limitations and uncertainties surrounding future CCS use in Australia and of the contribution CCS can make to mitigating emissions from the Australian stationary energy sector in the period to 2050. It considers two central questions: Is CCS a realistic option for emissions mitigation in Australia? Are Australian climate policies formulated to facilitate CCS deployment and optimise its potential contribution? The criteria employed in this thesis for answering these questions are restricted to those having an ascertainable causal impact on the timing, pace and ultimate scale of CCS deployment within Australia. The methodology used for the research is grounded in critical approaches and integrated assessment within a holistic, trans-disciplinary paradigm. / This thesis finds that under Australia’s existing climate policy framework it is unrealistic to expect CCS can contribute more than 75 million tonnes of CO2 per annum to emissions mitigation by 2050. Australia does have sufficient potential geological storage resources to expect some environmentally safe CCS infrastructure could be engineered over time, but commencement of large scale build-out is not likely before 2025. When CCS will become a commercial mitigation option in Australia is unpredictable and dependent more on the political economy of climate change than on Australian research, development and demonstration activities. / The thesis also finds that the existing climate policy framework is increasing rather than decreasing the risks to timing and usefulness of CCS even to the level of 75 million tonnes of CO2 per annum by 2050. This thesis concludes that Australian Governments are not developing the institutional capability to oversee a holistic decarbonisation of the stationary energy sector. This capability is required not only to address the risks to CCS deployment but also to prevent market failures that foreclose an optimal contribution from all other potential mitigation technologies. The thesis proposes that an Australian national CCS company be created with responsibility for CCS integration, transport and storage services in order to develop Australian capability rather than that of international corporations.

Forests are a key resource serving a multitude of functions such as providing income to forest owners, supplying industries with timber, protecting water resources, and maintaining biodiversity. Recently much attention has been given to the role of forests in the global carbon cycle and their management for increased carbon sequestration as a possible mitigation option against climate change. Furthermore, the use of harvested wood can contribute to the reduction of atmospheric carbon through (i) carbon sequestration in wood products, (ii) the substitution of non-wood products with wood products, and (iii) through the use of wood as a biofuel to replace fossil fuels. Forest resource managers are challenged by the task to balance these multiple while simultaneously meeting economic requirements and taking into consideration the demands of stakeholder groups. Additionally, risks and uncertainties with regard to uncontrollable external variables such as climate have to be considered in the decision making process. In this study a scientific stakeholder dialogue with forest-related stakeholder groups in the Federal State of Brandenburg was accomplished. The main results of this dialogue were the definition of major forest functions (carbon sequestration, groundwater recharge, biodiversity, and timber production) and priority setting among them by the stakeholders using the pair-wise comparison technique. The impact of different forest management strategies and climate change scenarios on the main functions of forest ecosystems were evaluated at the Kleinsee management unit in south-east Brandenburg. Forest management strategies were simulated over 100 years using the forest growth model 4C and a wood product model (WPM). A current climate scenario and two climate change scenarios based on global circulation models (GCMs) HadCM2 and ECHAM4 were applied. The climate change scenario positively influenced stand productivity, carbon sequestration, and income. The impact on the other forest functions was small. Furthermore, the overall utility of forest management strategies were compared under the priority settings of stakeholders by a multi-criteria analysis (MCA) method. Significant differences in priority setting and the choice of an adequate management strategy were found for the environmentalists on one side and the more economy-oriented forest managers of public and private owned forests on the other side. From an ecological perspective, a conservation strategy would be preferable under all climate scenarios, but the business as usual management would also fit the expectations under the current climate. In contrast, a forest manager in public-owned forests or a private forest owner would prefer a management strategy with an intermediate thinning intensity and a high share of pine stands to enhance income from timber production while maintaining the other forest functions. The analysis served as an example for the combined application of simulation tools and a MCA method for the evaluation of management strategies under multi-purpose and multi-user settings with changing climatic conditions. Another focus was set on quantifying the overall effect of forest management on carbon sequestration in the forest sector and the wood industry sector plus substitution effects. To achieve this objective, the carbon emission reduction potential of material and energy substitution (Smat and Sen) was estimated based on a literature review. On average, for each tonne of dry wood used in a wood product substituting a non-wood product, 0.71 fewer tonnes of fossil carbon are emitted into to the atmosphere. Based on Smat and Sen, the calculation of the carbon emission reduction through substitution was implemented in the WPM. Carbon sequestration and substitution effects of management strategies were simulated at three local scales using the WPM and the forest growth models 4C (management unit level) or EFISCEN (federal state of Brandenburg and Germany). An investigation was conducted on the influence of uncertainties in the initialisation of the WPM, Smat, and basic conditions of the wood product sector on carbon sequestration. Results showed that carbon sequestration in the wood industry sector plus substitution effects exceeded sequestration in the forest sector. In contrast to the carbon pools in the forest sector, which acted as sink or source, the substitution effects continually reduced carbon emission as long as forests are managed and timber is harvested. The main climate protection function was investigated for energy substitution which accounted for about half of the total carbon sequestration, followed by carbon storage in landfills. In Germany, the absolute annual carbon sequestration in the forest and wood industry sector plus substitution effects was 19.9 Mt C. Over 50 years the wood industry sector contributed 70% of the total carbon sequestration plus substitution effects. / Wälder beeinflussen in vielfältiger Weise unser Leben. Für den Waldbesitzer sind sie Einkommensquelle, die Holzindustrie versorgen sie mit dem Rohstoff, aus dem unzählige Dinge für den täglichen Bedarfs hergestellt werden, wie zum Beispiel Baumaterialien, Möbel, Gartengeräte, Spielzeug und Papier. Außerdem versorgen Wälder uns mit sauberem Grundwasser, sind Lebensraum für Pflanzen und Tiere und tragen somit zum Erhalt der Artenvielfalt bei. Nicht zuletzt beeinflussen Wälder das Klimasystem, da sie der Atmosphäre das Treibhausgas CO2 entziehen und Kohlenstoff in Biomasse und Boden speichern. Förster stehen nun vor der anspruchsvollen Aufgabe, eine Balance zwischen den vielfältigen und oft auch gegensätzlichen Waldfunktionen zu finden und die Ansprüche von Interessengruppen wahrzunehmen. Zusätzlich müssen im waldbaulichen Entscheidungsprozess Risiken und Unsicherheiten durch unberechenbare externe Faktoren, wie das Klima, beachtet werden. Ziel der Arbeit war es, den Einfluss von Klima und Waldbaustrategien auf Waldfunktionen zu untersuchen. Als Testgebiet fungierte das Revier Kleinsee im Südosten Brandenburgs, in dem Kiefern- und Eichenbestände vorherrschen. In einem wissenschaftlichen Dialog mit Angestellten der Forstbehörde, Privatwaldbesitzern, Vertretern von Naturschutzverbänden sowie Wissenschaftlern definierten die Teilnehmer die wichtigsten Waldfunktionen: Kohlenstoffspeicherung, Grundwasserneubildung, Biodiversität und Holzproduktion. Die Simulationen wurden mit Hilfe des Waldwachstumsmodells 4C und einem neu implementierten Holzproduktmodell (WPM) über einen Zeitraum von 100 Jahren durchgeführt. Dabei wurden den heutigen Klimabedingungen zwei Klimaänderungsszenarien gegenübergestellt, die auf den globalen Zirkulationsmodellen HadCM2 und ECHAM4 basieren. Es stellte sich heraus, dass unter den angenommenen Klimaänderungen das Wachstum der Bestände steigt und sich damit die Kohlenstoffspeicherung und der Ertrag aus Holzernten erhöht, wohingegen Biodiversität und Grundwasserneubildung nur sehr gering beeinflusst werden. Der Nutzen der Waldbewirtschaftungsstrategien für drei Interessensgruppen (Forstbehörde, private Waldbesitzer, Naturschutzvereine) wurde mit einer multikriteriellen Analysemethode bewertet. Dabei unterschieden sich die Rangfolge und Gewichtung der einzelnen Waldfunktionen sowie die daraus resultierende Wahl der Waldbaustrategien zwischen den Naturschützern einerseits sowie den stärker ökonomisch orientierten Landeswaldförstern und privaten Waldbesitzern anderseits. Naturschutzvereine bevorzugen das Einstellen der Waldbewirtschaftung, aber auch die aktuelle Waldbaustrategie, mit mäßiger Durchforstungsintensität und einem hohen Anteil an Eichenbeständen entspricht ihren Zielsetzungen. Dagegen lag die Präferenz der Landeswaldförster sowie privaten Waldbesitzer auf einer Walbaustrategie mit einem hohen Anteil an Kiefernbeständen, um den Ertrag unter Beachtung der anderen Waldfunktionen zu steigern. Als Fazit geht aus dieser Teilstudie hervor, dass die Bewertung von Waldbaustrategien hinsichtlich ihrer Eignung für eine multifunktionale Waldbewirtschaftung unter Beachtung von Ansprüchen verschiedener Interessengruppen und ungewissen klimatischen Bedingungen unter Verwendung von 4C und einer multikriteriellen Analysemethode sehr gut möglich ist. Besonderes Augenmerk galt dem Einfluss von Waldbaustrategien auf den Kohlenstoffkreislauf, wobei nicht nur die Kohlenstoffspeicherung im Wald, sondern auch in Holzprodukten, sowie die Verringerung von CO2-Emissionen durch energetische und stoffliche Nutzung von Holz betrachtet wurden. Die potentielle Reduktion von CO2-Emissionen durch das Ersetzen von Erzeugnissen und Energie aus nicht nachwachsenden Rohstoffen durch Holz (Smat und Sen) wurde basierend auf Daten verschiedener Studien geschätzt. Eine Sensitivitätsanalyse untersuchte Unsicherheiten bei der Initialisierung des WPMs und der Berechung von Smat. Verschiedene Szenarien führten zu einem besseren Verständnis dafür, wie sich Änderungen im Energiesektor und Holzproduktsektor auf das Potential, Kohlenstoff zu speichern bzw. CO2-Emissionen zu verringen auswirken. Die Ergebnisse zeigen, dass die Reduzierung von CO2-Emissionen im Holzproduktsektor durch die Nutzung von Holz als Werkstoff und Brennstoff höher ist als durch die Akkumulation von Kohlenstoff im Wald. Im Gegensatz zu den Kohlenstoffspeichern im Wald, die sowohl Quellen als auch Senken sein können, werden durch die Nutzung von Holz CO2-Emissionen verringert, solange im Zuge der Waldbewirtschaftung Holz für die Weiterverarbeitung zur Verfügung gestellt wird. Simulationen auf Bundesebene ergaben, dass in Deutschland die Forst- und Holzwirtschaft jährlich dazu beitragen die CO2-Emissionen um 19,9 Mt Kohlenstoff zu verringern, wobei 70% auf die Holzindustrie und den Substitutionseffekt entfallen.

Green chemistry principles have been applied to the enhancement of two industrial chemistry problems. An industrially used reaction to form alcohols from aldehydes and ketones, the Meerwein-Ponndorf-Verley reduction, was improved by introducing a new catalyst Al(OtBu)₃. Due to the lower state of aggregation of this catalyst versus the conventional Al(OiPr)₃ catalyst, reduction rates were found to be faster in both pure iPrOH and mixed solvent systems for three model compounds: benzaldehyde, acetophenone, and a complex, chiral ketone, (S)-CMK. This allowed for the successful implementation of two important milestones; lowering the amount of catalyst needed necessary to complete the reactions (an economic benefit and lower waste) and the conversion from traditional batch reactions to continuous flow (a processing benefit) whereby reactions can be scaled-out rather than scaled-up. Another industrially important field of research that was focused on was CO₂ capture. High energy demands from current CO₂ capture methods such as aqueous amine solvents, specifically from coal-fired power plant flue gas, led to the development of non-aqueous reversible ionic liquids based on silylated amines. Structural modifications of the substitution around the silicon atom, the length of the alkyl chain bonding the silicon and amine, branching along the alkyl backbone, and investigating secondary and primary amines within this class of silylated amines were completed. These amines were reacted with CO₂ and the CO₂ capacity, the ionic liquid viscosity, reversal temperature and reaction enthalpy were all considered as a function of structure. In all cases the capacity was found to be not only greater than that of monethanolamine, an industrial standard, but higher than theoretical predictions through the formation of carbamic acid. Viscosity, reversal temperature, and reaction enthalpy were all found to be tunable through structure. These modifications gave significant insight into the necessary direction for optimization of these solvents as energy-efficient replacements of current CO₂ capture technology.

Woody plant invasion of grasslands is prevalent worldwide, but the biogeochemical consequences of this vegetation shift remain largely unquantified. In the Rio Grande Plains, TX, grasslands and savannas dominated by C4 grasses have undergone succession over the past century to subtropical thorn woodlands dominated by C3 trees/shrubs. To elucidate mechanisms of soil organic carbon (SOC) and soil total N (STN) storage and dynamics in this ecosystem, I measured the mass and isotopic composition (δ13C, δ15N) of C and N in whole-soil and soil size/density fractions in chronosequences consisting of remnant grasslands (Time 0) and woody plant stands ranging in age from 10-130 years. Rates of SOC and STN storage averaged 10-30 g C m-2yr-1 and 1-3 g N m-2yr-1, respectively. These accumulation rates increased soil C and N pools 80-200% following woody encroachment. Soil microbial biomass (SMB-C) also increased after woody invasion. Decreasing Cmic/C org and higher qCO2 in woodlands relative to grasslands suggests that woody litter is of poorer quality than grassland litter. Greater SOC and STN following woody invasion may also be due to increased protection of organic matter by stable soil structure. Soil aggregation increased following woody encroachment; however, most of the C and N accumulated in free particulate organic matter (POM) fractions not protected within aggregates. Mean residence times (MRTs) of soil fractions were calculated based on changes in their δ13C with time after woody encroachment. Free POM had the shortest average MRTs (30 years) and silt+clay the longest (360 years). Fine POM had MRTs of about 60 years, reflecting protection by location within aggregates. δ15N values of soil fractions were positively correlated with their MRTs, suggesting that higher δ15N values reflect an increased degree of humification. Increases in SOC and STN are probably being sustained by greater inputs, slower turnover of POM (some biochemical recalcitrance), and protection of organic matter in aggregates and association with silt and clay. Grassland-to-woodland conversion during the past century has been geographically extensive in grassland ecosystems worldwide, suggesting that changes in soil C and N dynamics and storage documented here could have significance for global C and N cycles.

The bioavailability of iron is limited by the solubility of Fe(III) at circumneutral pH. In the High Nutrient-Low Chlorophyll (HNLC) zones of the ocean, the natural or anthropogenic addition of iron stimulates primary productivity and consumes carbon dioxide. As a result, iron fertilization has been proposed to mitigate anthropogenic carbon emissions and lower global temperatures. The natural sources of iron to the ocean are not fully constrained and include eolian depositions as well as inputs from continental shelf sediments, rivers, hydrothermal vents, and icebergs. Regardless of their source, the effectiveness of iron additions in promoting carbon fixation depends on the presence of organic ligands either natural or produced by microorganisms that stabilize or solubilize Fe(III) at neutral pH. For example, siderophores are well known to be expressed extracellularly by prokaryotes in the photic zones of the oceans to increase the bioavailability of iron. In this dissertation, the production of iron nanoparticles is demonstrated in vent fluids from the 90 North hydrothermal system. These iron nanoparticles may either catalyze the oxidation of sulfide to thiosulfate and produce a potential electron acceptor for microbial respiration or provide a source of iron that stimulates primary production at great distances from the hydrothermal vents. In addition, dissolved iron under the form of soluble organic-Fe(III) complexes is demonstrated to constitute a significant source of iron in estuarine sediments that receive large amounts of particulate iron from flocculation and precipitation at the salinity transition of this estuary. A novel competitive ligand equilibration absorptive cathodic stripping voltammetry (CLE-ACSV) technique reveals that the speciation of iron changes from largely colloidal or particulate in the upper estuary to truly dissolved organic-Fe(III) in the lower estuary. It is also demonstrated that organic-Fe(III) complexes are produced far below the sediment-water interface, suggesting that dissimilatory iron-reducing bacteria may play an important role in their production. These complexes then diffuse across the sediment-water interface and provide a significant source of iron to the continental shelf. The mechanism of reduction of iron oxides by iron-reducing bacteria is not fully understood and presents a unique physiological problem for the organism, as the terminal reductase has to transfer electrons to a solid electron acceptor. In this dissertation, it is demonstrated for the first time using random mutagenesis that the respiration of solid Fe(III) oxides by Shewanella oneidensis, a model iron-reducing prokaryote, first proceeds through a non-reductive dissolution step involving organic ligands that are released extracellularly by the cells. These soluble complexes are then reduced by the organism to produce Fe(II) and recycle the ligand for additional solubilization. Incubations with deletion mutants of the proteins involved in the respiration of Fe(III) revealed that the type-II secretion system, which translocates proteins on the outer membrane of gram-negative bacteria, is involved in the production of organic-Fe(III) complexes by secreting an endogenous iron-solubilizing ligand or a protein involved in the biosynthesis of this ligand on the outer membrane. In addition, periplasmic decaheme cytochromes produced by Shewanella appear to be involved in the mechanism of production of the endogenous organic ligand either directly or through a sensing mechanism that controls its production. In turn, two decaheme cytochromes positioned on the outer-membrane and hypothesized to be involved in the electron transfer to the mineral surface do not appear to be involved in the solubilization mechanism, suggesting either that the cells regulate the ligand production via periplasmic sensing systems or that these cytochromes are not involved in the solubilization mechanism. Altogether this research shows the production of organic-Fe(III) complexes in sediments generates a significant flux of dissolved iron to support primary production in continental shelf waters and that these complexes may be partly produced by iron-reducing bacteria. Indeed, experiments with a model organism demonstrate dissimilatory iron reducing bacteria produce endogenous organic ligands with high iron-binding constants to non-reductively solubilize iron oxides during the anaerobic respiration of iron oxides. The organic ligand is apparently recycled several times to minimize the energy cost associated with its biosynthesis. These findings demonstrate that the solubilization of iron oxides by organic ligands may be an important, yet underappreciated process in aquatic systems.

The Little Grand Wash normal fault near Green River, eastern Utah, hosts a series of naturally occurring CO₂ seeps in the form of active and extinct CO₂-charged springs distributed along the fault zone. I have studied the association of fault structure with CO₂-related alteration as an analogue for the long-term (1,000- to 10,000-year) effects of leakage through faults in CO₂ sequestration reservoirs. Structure and alteration in a portion of the Little Grand Wash fault zone were mapped at a 1:700 scale in order to determine the association of faulting with CO₂-related diagenesis. I combined structural and diagenetic mapping were combined with laboratory analyses of mineralogical, isotopic and textural changes in order to assess controls on the migration of CO₂ traveling up the fault and its effects on the fault itself. The fault zone is 200 m wide at its widest and contains 4-5 major subparallel fault segments that form multiple soft- and hard-linked relay ramps. The area includes a travertine deposit and related sandstone alteration: outcrop-visible coloration, porosity-occluding calcite cement and veins occasionally so abundant that they obliterate the rock fabric. Structural mapping shows that the travertine is located at an intersection of major fault segments constituting the hard link of a 450-meter-long relay ramp. Sandstone alteration is confirmed to be related to the CO₂ seep by mapping its distribution, which shows a decrease in concentration away from the travertine, and by the unique isotopic signature of calcite cement near the travertine. At distances greater than 25 m from the travertine intense alteration disappears, though scattered fault-subparallel veins and patchy, burial-related calcite cement remain. Intense alteration is limited to major fault overlaps and does not permeate the fault zone along its entire length, nor does it extend outside the zone. This indicates that rising CO₂-laden fluids do not flow uniformly through the entire fault zone, but that vertical flow is channeled at fault intersections. In thin section, porosity near the travertine has been extensively or completely occluded by calcite cement. Permeability in some conduit samples is less than 1 mD, three or four orders of magnitude lower than sandstone away from the travertine. In active CO₂ conduits, such reduction in porosity and permeability would occlude the preferred flow conduit and ultimately restrict upward flow of CO₂-charged water. X-ray diffraction detects small amounts of goethite and hematite and a decrease in chlorite-smectite in altered conduit sandstones. Calcite is abundant, but many authigenic minerals predicted by geochemical models of CO₂ influx into sandstone reservoirs are not observed, including kaolinite, aragonite, dolomite, siderite, ankerite or dawsonite. This difference between observed and predicted mineral occurrence likely results from differences in mineral kinetics between natural and laboratory systems. Prediction of leakage risk based on fault geometry improves the ability to assess the suitability of potential carbon sequestration reservoirs, many of which will be faulted. The point seep nature of leakage through a fault zone limits the amount of CO₂ that can escape over time and also enables targeted surface monitoring for CO₂ escape into the atmosphere--both critical for ensuring the effectiveness of injection projects and earning the trust necessary for carbon sequestration to gain public acceptance. The point seep nature of leakage also accelerates the rate at which conduits may seal through mineralization, since precipitation from a large volume of fluid is focused in a narrow conduit. The presence of multiple fossil and active seep locations along the Little Grand Wash fault, active at different times in the geologic past, indicates that cementation may be effective in sealing single conduits but that fault systems with complex geometry such as Little Grand Wash may continue to leak for a long period of time. / text

Populations of black mangroves (Avicennia sp.) are hypothesized to expand their latitudinal range with global climate change in the 21st century, induced by a reduction in the frequency and severity of coastal freezes, which are known to limit mangrove colony extent and individual tree size, as well as an overall warmer climate. The Gulf of Mexico is located at the northward limit of black mangrove habitat and is therefore a prime candidate for population expansion with global warming. This expansion may come at the expense of existing Gulf coastal saline wetlands that are dominantly Spartina spp. marsh grasses. The present study was conducted to focus, not on the extent to date of this replacement, but to examine the potential implications of a marsh to mangrove transition in Gulf wetlands, specifically 1) resistance to accelerating eustatic sea level rise (ESLR) rates, 2) wetland resistance to wave attack in large storms (increased cyclonic storm frequency/intensity is predicted with future climate warming), and 3) organic carbon sequestration and wetland soil geochemistry. Field sites of adjacent and intergrown Avicennia mangrove and Spartina marsh populations in similar geomorphological setting were selected in back-barrier areas near Port Aransas and Galveston, TX (two sites each) as part of a larger-scale planned study of the full latitudinal transition of the western Gulf funded by the National Institute for Climate Change Research (U.S. Department of Energy). The reconnaissance conducted for site surveys show that black mangrove populations in this part of Texas are clustered near inlet areas, suggesting seed transport vectors are a major control on colony establishment, and likely, on the potential rapidity of wetland habitat replacement. Resistance to ESLR was tested by 1) creating high-accuracy (±1 cm) elevation maps over ~5,000 m² areas of adjacent mangrove and marsh areas, and 2) measuring mineral and organic matter accumulation rates (Pb/Cs radiotracer geochronology, loss on ignition) from auger cores. Elevation surveys in Port Aransas indicate mangrove vegetated areas are 4 cm higher in elevation than surrounding marsh on an average regional scale, and 1 to 2 cm higher at the individual mangrove scale: at the Galveston sites, any trend is complicated by the area's pre-existing geomorphology and the relative youth of the mangrove colonies. ¹³⁷Cs accumulation rates and loss on ignition data indicate that mineral trapping is 4.1 times higher and sediment organics are 1.7 times lower in mangroves at Port Aransas; no such definable trends exist at the Galveston sites or in calculated ²¹⁰Pb sediment accumulation rates. This additional mineral particle trapping in mangroves does not differ in grain size character from marsh mineral accumulation. Elevation change may also be effected by root volume displacement: live root weight measurements in the rooted horizon (~0 to 20 cm depth) are consistently higher in mangrove cores from Port Aransas and the site at the west end of Galveston Island. Port Aransas porosities are lower in mangrove rooted horizons, with a corresponding increase in sediment strength (measured by shear vane in the cores), suggesting mangrove intervals may be more resistant to wave-induced erosion during storm events. Port Aransas mangroves exhibit higher pore water redox potentials and salinities over entire core depths and depressed pH over rooted intervals, suggesting a distinct diagenetic environment exists relative to marsh sites. Increased salinities and higher redox potentials may be a function of the rooting network, which introduces oxygen into the sediment and focuses evapo-transpiration and salt exclusion within this zone: this may prove advantageous when competing with marsh grasses by elevating salinities to levels that are toxic for Spartina. Trends observed in the more mature systems of Port Aransas are generally absent at the Galveston sites, suggesting the youth and physically shorter stature of these systems means they have not yet established a unique sediment signature. / text

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