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

No description available.

The Canadian greenhouse gas offset system was proposed and developed with the objective of assisting Canada in achieving its Kyoto target by means of low cost emission reduction. This study estimates the potential of agricultural soils in Canada to provide carbon credits. Carbon sequestration practices such as moderate till, no-till and perennial crop activities were considered in the analysis. Crops under different tillage regimes, hay and alfalfa were also included in the study. Simulation analysis was undertaken using the Canadian Regional Agricultural Model (CRAM) for carbon prices ranging from $5 to $100/t of CO2e. Carbon credits generated as a result of the sequestration activities were estimated by endogenizing a carbon price for the sequestration activity into the CRAM model. The analysis was done regionally, provincially, and nationally. Two scenarios were investigated; one that included tillage practices and perennial crops (Policy All) and the other that only included tillage practices (Policy Till). Cropping pattern changes, carbon sequestration levels, carbon revenues, and adoption rates were estimated in the simulation. In addition, the role of transaction costs in the offset system was also examined. / The results of the simulation indicated that crop shifts towards hay and alfalfa occurred in the Policy All scenario, while practice shifts towards moderate and no-till occurred in the Policy Till scenario. Simulation analysis indicated that carbon sequestration levels vary by province and region. Among the provinces, the Prairie provinces had the highest carbon sequestration levels ranging from 50 percent under the Policy Till scenario, while under the Policy All scenario it was close to 97 percent. Nationally at a medium price of $15/t of CO2 approximately 1.08 Mt of CO2 and 0.11 Mt of CO2 were sequestered under Policy All and Policy Till scenario. When transaction costs were included in the analysis, approximately 30 to 40 percent less sequestration from the baseline was estimated. The results varied by province and region.

Both physical circulation and biogeochemical characteristics are unique in the Southern Ocean (SO) region, and are fundamentally different from those of the northern hemisphere. Moreover, according to previous research, the oceanic response to the trend of the Southern Annual Mode (SAM) has profound impacts on the future oceanic uptake of carbon dioxide in the SO. In other words, the climate and circulation of the SO are strongly coupled to the overlying atmospheric variability. However, while we have understanding on the SO physical circulation and have the ability to predict the future changes of the SO climate and physical processes, the link between the SO physical processes, the air-sea carbon flux, and correlated climate variability remains unknown. Even though scientists have been studying the spatial and temporal variability of the SO carbon flux and the associated biogeochemical processes, the spatial patterns and the magnitudes of the air-sea carbon flux do not agree between models and observations. Therefore, in this study, we utilized a modified version of a general circulation model (GCM) to performed realistic simulations of the SO carbon on seasonal to interannual timescales, and focused on the crucial physical and biogeochemical processes that control the carbon flux. The spatial pattern and the seasonal cycle of the air-sea carbon dioxide flux is calculated, and is broadly consistent with the climatological observations. The variability of air-sea carbon flux is mainly controlled by the gas exchange rate and the partial pressure of carbon dioxide, which is in turn controlled by the compensating changes in temperature and dissolved inorganic carbon. We investigated the seasonal variability of dissolved inorganic carbon based on different regional processes. Furthermore, we also investigated the dynamical adjustment of the surface carbon flux in response to the different gas exchange parameterizations, and conclude that parameterization has little impact on spatially integrated carbon flux. Our simulation well captured the SO carbon cycle variability on seasonal to interannual timescales, and we will improve our model by employ a better scheme of nutrient cycle, and consider more nutrients as well as ecological processes in our future study.

Saltwater marshes in the Bay of Fundy act as greenhouse gases sinks and reservoirs by fixing atmospheric carbon dioxide and storing it in carbon rich deposits. There are approximately 3,131.5 hectares of saltwater marsh in the Bay of Fundy, of which 958 ha are currently owned by the government or conservation organizations and 2,173.5 ha are owned by private landowners. A multiple bounded discrete choice contingent valuation survey was conducted to estimate landowners' willingness to accept compensation for selling their saltwater marshes to a conservation program. A multiple bounded model developed by Gregory Poe and Michael Welsh (1995) was used to analyze the responses. Mean willingness to accept compensation for one hectare of saltwater marsh was estimated to be $1,004.22, and aggregate willingness to accept compensation for the total of 2,173.5 ha of saltwater marsh owned by private landowners was approximately $2,180,000. Using these estimates and the rate of carbon dioxide-equivalent absorption of saltwater marshes, the opportunity cost of one tonne of carbon dioxide-equivalent sequestered by saltwater marshes in the Bay of Fundy was calculated to range between $16.70 and $19.95. Decision-makers can use this result for policy purposes concerning the achievement by Canada of its greenhouse gases emission reduction commitment under the Kyoto Protocol (1997).

CO2 sequestration is one of the proposed methods for reducing anthropogenic CO2 emissions to the atmosphere and therefore mitigating global climate change. Few studies on storing CO2 in an aquifer have been conducted on a regional scale. This study offers a conceptual approach to increasing the storage efficiency of CO2 injection in saline formations and investigates what an actual CO2 storage project might entail using field data for the Woodbine aquifer in East Texas. The study considers three aquifer management strategies for injecting CO2 emissions from nearby coal-fired power plants into the Woodbine aquifer. The aquifer management strategies studied are bulk CO2 injection, and two CO2-brine displacement strategies. A conceptual model performed with homogeneous and average reservoir properties reveals that bulk injection of CO2 pressurizes the aquifer, has a storage efficiency of 0.46% and can only last for 20 years without risk of fracturing the CO2 injection wells. The CO2-brine displacement strategy can continue injecting CO2 for as many as 240 years until CO2 begins to break through in the production wells. This offers 12 times greater CO2 storage efficiency than the bulk injection strategy. A full field simulation with a geological model based on existing aquifer data validates the storage capacity claims made by the conceptual model. A key feature in the geological model is the Mexia-Talco fault system that serves as a likely boundary between the saline aquifer region suitable for CO2 storage and an updip fresh water region. Simulation results show that CO2 does not leak into the fresh water region of the iv aquifer after 1000 years of monitoring if the faults have zero transmissibility, but a negligible volume of brine eventually gets through the mostly sealing fault system as pressure across the faults slowly equilibrates during the monitoring period. However, for fault transmissibilities of 0.1 and 1, both brine and CO2 leak into the fresh water aquifer in increasing amounts for both bulk injection and CO2-brine displacement strategies. In addition, brine production wells draw some fresh water into the saline aquifer if the Mexia-Talco fault system is not sealing. A CO2 storage project in the Woodbine aquifer would impact as many as 15 counties with high-pressure CO2 pipelines stretching as long as 875 km from the CO2 source to the injection site. The required percentage of power plant energy capacity was 7.43% for bulk injection, 7.9% for the external brine disposal case, and 10.2% for the internal saturated brine injection case. The estimated total cost was $0.00132–$0.00146/kWh for the bulk injection, $0.00191–$0.00211/kWh for the external brine disposal case, and $0.0019–$0.00209/kWh for the internal saturated brine injection case.

Thesis (doctoral)--Swedish University of Agricultural Sciences, 2007. / Thesis documentation sheet inserted. Includes appendix of four papers and manuscripts, three co-authored with others. Includes bibliographical references. Also issued electronically via World Wide Web in PDF format; online version lacks appendix.