The goal of this study is to develop a gradient-independent method for modeling surface gas flux using surface gas concentration data. The proposed method is built on the relationship between gas flux and the time history of surface gas concentration, known as half-order derivative (HOD), when the transport of gas in the boundary layer is described by a diffusion equation. The new model is tested using in-situ data of CO2 concentration time series at half hour (or hour) intervals from Ameriflux Network at several locations in US, Canada, Mexico and Brazil to estimate CO2 fluxes. In this research the estimated CO2 flux using HOD method are compared with observed CO2 fluxes from four study sites out of 160+ sites with diverse vegetation cover, geographic and climatic conditions to test the generality of model within reasonable endeavor. The sites are Cedar Bridge National Forest, New Jersey, Delta Junction 1920 Control, Alaska, Lucky Hills Shrub land, Arizona, and LBA Tapajos Mature Forest, Brazil. The modeled CO2 flux demonstrates close agreement with field observations confirming the usefulness and potential of HOD model for estimating CO2 gas fluxes.

Nitrous oxide (N2O) is a potent greenhouse gas (GHG) which is released naturally into the atmosphere as a by-product of the microbial processes of nitrification and denitrification. Agricultural activities are believed to account for up to 80% of anthropogenic N2O emissions at a global scale; however, these estimates are prone to large uncertainties due to the large temporal and spatial variability associated with flux measurements. This thesis contains five studies which aimed to improve the ability to measure and predict N2O emissions from agricultural activities. A closed loop dynamic chamber was developed using a quantum cascade laser (QCL). This method provided high precision chamber measurements of N2O flux from soils with a detection limit below 4 μg N2O-N m-2 h-1. Using the dynamic chamber method allowed for a detailed investigation of uncertainties in individual measurements including contributions from regression fitting, temperature and pressure. The lack of negative fluxes measured that were outwith the detection limits of the methodology (0.3% of all measurements) highlighted that the uptake of N2O reported in some previous literature is likely to have been the result of detection limits of measurement methods applied. Spatial variability of N2O flux was investigated at the plot, field and farm scale. Fluxes were measured from a grassland field plot before and after a tillage event. These measurements highlighted the large spatially variability present in N2O fluxes from agricultural soils. Fluxes varied by up to three orders of magnitude over distances less than 5 metres after the tillage event. A field scale experiment carried out on grazed grassland investigated relationships between soil properties and N2O flux. This study found that N2O emissions correlated strongly with available nitrogen content in the soil and that animal waste was likely responsible for the spatial variability of N2O flux observed at the field scale. A farm scale inventory of N2O emissions was carried out investigating several large point sources of N2O and emissions from the wider field coverage. The inventory estimates that nitrogen fertiliser application is the single largest N2O source from the livestock farm accounting for 49% of annual emissions.

Degradation of permafrost in peatlands can convert forested peat plateaus to inundated collapse bogs. Due to increased unfrozen soil carbon stocks and more saturated conditions, collapse bogs can potentially be large emitters of methane. Using a network of bubble traps permanently installed in peat, I tested several hypotheses about controls on ebullition in collapse bogs with varying time since thaw in interior Alaska. Ebullition increased during the growing season, likely due to increased substrate availability and warmer soils. Bubbles were found primarily in shallow peat layers, and were dominated by modern carbon. Ebullition hot spots were associated with high sedge density throughout the collapse sites. Episodic ebullition occurred during atmospheric pressure changes. Overall, my study demonstrated that permafrost thaw in peatlands will result in methane emissions through ebullition that include both young and old carbon, contradictory to the generally accepted paradigm; that ebullition in peatlands is solely a surface process.

Research into the mechanisms responsible for the lasting, cyclic activity at Masaya volcano can lead to a better understanding of persistently degassing volcanoes. This study is greatly enhanced by the integration of dynamic micro-gravity, deformation and gas flux measurements. The acquisition of extended temporal and spatial geophysical data will also allow for the development of robust models for the dynamics of magmatic systems. Masaya volcano, Nicaragua, is one of the most active systems in Central America, making it an excellent natural laboratory for this study. It is noted for repeated episodes of lava lake formation, strong degassing and subsequent quiescence. Ground-based geophysical measurements show two episodes of similar magnitude gravity decreases in 1993-1994 and 1997-1999, separated by a period of minor gravity increase. A major increase in S02 gas flux from 1997-1999 correlates well with the most recent episode of gravity decrease. The gravity changes are not accompanied by deformation in the summit areas and are interpreted in terms of sub-surface density changes. The persistent degassing at Masaya suggests that up to -15 krrr' of magma may have degassed over the last 150 years, only a minute fraction of which has been erupted. Furthermore, thermal flux calculations suggest that 0.5 krrr' of magma (the estimated volume of the shallow reservoir) would cool from liquidus to just above solidus temperatures in only 5 years. The high rates of degassing and cooling at open-system volcanoes such as Masaya raise questions as to the ultimate fate of this degassed and cooled magma. A number of models have been proposed to explain this, but the most likely mechanism to explain persistent activity at Masaya and other similar volcanoes is convective removal of cooled and degassed magma and subsequent recharge by volatile-rich magma from depth. Another fundamental question in modem volcanology concerns the manner in which a volcanic eruption is triggered; the intrusion of fresh magma into a reservoir is thought to be a key component. The amount by which previously ponded reservoir magma interacts with a newly intruded magma will determine the nature and rate of eruption as well as the chemistry of erupted lavas and shallow dykes. The physics of this interaction can be investigated through a conventional monitoring procedure that incorporates the Mogi model relating ground deformation (~) to changes in volume of a magma reservoir. Gravity changes (.1.g)combined with ground deformation provides information on magma reservoir mass changes. Models developed here predict how, during inflation, the observed .1.gI~ gradient will evolve as a volcano develops from a state of dormancy through unrest into a state of explosive activity.

Recent work has described how gas exchange can occur through sea ice. First, carbon fluxes over sea ice surfaces have been measured. Second, sea ice brine has an elevated capacity over seawater to absorb CO2(g) due to its cold temperature and chemical equilibrium promoting carbon phase changes. Sea ice pCO2 profiles were collected using a new method of remotely sampling gas in situ via diffusive membranes placed within growing sea ice. Gas analysis was complimented by measurements of local meteorology and ice chemistry. The work was part of the CASES 2004 project. The observed elevation in sea ice pCO2 coupled with the mobility of the brine points to the role that brine plays in Arctic carbon transport. The gas transport links the Arctic atmosphere and ocean and indicates that a thinning and receding ice cover may not result in creating a negative feedback to the increasing atmospheric CO2(g) concentration. / October 2008

Recent work has described how gas exchange can occur through sea ice. First, carbon fluxes over sea ice surfaces have been measured. Second, sea ice brine has an elevated capacity over seawater to absorb CO2(g) due to its cold temperature and chemical equilibrium promoting carbon phase changes. Sea ice pCO2 profiles were collected using a new method of remotely sampling gas in situ via diffusive membranes placed within growing sea ice. Gas analysis was complimented by measurements of local meteorology and ice chemistry. The work was part of the CASES 2004 project. The observed elevation in sea ice pCO2 coupled with the mobility of the brine points to the role that brine plays in Arctic carbon transport. The gas transport links the Arctic atmosphere and ocean and indicates that a thinning and receding ice cover may not result in creating a negative feedback to the increasing atmospheric CO2(g) concentration.

Recent work has described how gas exchange can occur through sea ice. First, carbon fluxes over sea ice surfaces have been measured. Second, sea ice brine has an elevated capacity over seawater to absorb CO2(g) due to its cold temperature and chemical equilibrium promoting carbon phase changes. Sea ice pCO2 profiles were collected using a new method of remotely sampling gas in situ via diffusive membranes placed within growing sea ice. Gas analysis was complimented by measurements of local meteorology and ice chemistry. The work was part of the CASES 2004 project. The observed elevation in sea ice pCO2 coupled with the mobility of the brine points to the role that brine plays in Arctic carbon transport. The gas transport links the Arctic atmosphere and ocean and indicates that a thinning and receding ice cover may not result in creating a negative feedback to the increasing atmospheric CO2(g) concentration.

A series of detailed laboratory investigations were conducted to examine low solubility gas transfer across wind-forced wavy air-water interfaces. The study focuses on the increase in gas flux associated with the microphysical interfacial wind momentum exchange and the complex wave coupled hydrodynamics. Key elements of the laboratory investigations included the measurement of hydrodynamic behaviour within the aqueous viscous sub-layer using a particle image velocimetry (PIV) system and the development of a Laser Induced Fluorescent (LIF) system capable of measuring reliable dissolved oxygen concentration profiles to within 28??m of the air-water interface. Major achievements and findings included: 1. The first phase resolved gas flux measurements along wind forced microscale waves, indicating the highest mean gas fluxes are located in the wave troughs. This finding demonstrated the relative importance of wave orbital straining in gas flux enhancement; a wave coupled hydrodynamic process whose significance has previously been neglected. 2. The relative contributions to gas flux from wind shear, wave orbital straining, increased surface area of the waves, parasitic capillary ripples and microscale breaking are quantified with respect to friction velocity, wave steepness and an efficiency of microscale wave breaking. The parasitic capillary ripples are shown to have a negligible role in gas enhancement. A hybrid model is developed to estimate the gas flux based on both wind and wave characteristics. 3. Gas enhancement due to microscale wave breaking and the significance of the highly localised subduction at the toe of the spilling region on the leeward face of the wave crests was investigated using data from the LIF experiments. The highly localised subduction was shown to substantially reduce the thickness of the diffusion sub-layer, resulting in an increase in gas flux when waves transitioned from the incipient breaking to the microscale breaking wave form. 4. Consideration of previously unidentified optical distortions in LIF imagery due to non-linear effects is presented that is critical for robust LIF data processing and experimental design. A formal mathematical description of optical distortions has been developed and presented.

Hydrothermal systems change in response to volcanic activity, and in turn may be sensitive indicators of volcanic activity. Fumaroles are a surface manifestation of this interaction. We use time series of soil temperature data and numerical models of the hydrothermal system to investigate volcanic, hydrologic and geologic controls on this diffuse degassing. Soil temperatures were measured in a low-temperature fumarole field located 3.5 km from the summit of Masaya volcano, Nicaragua. They respond rapidly, on a time scale of minutes, to changes in volcanic activity also manifested at the summit vent. The soil temperature response is repetitive and complex, and is characterized by a broad frequency signal allowing it to be distinguished from meteorologic trends. Geophysical data reveal subsurface faults that affect the transport of fumarole gases. Numerical modeling shows that these relatively impermeable faults enhance flow through the footwall. On a larger scale, modeling suggests that uniform injection of fluid at depth causes groundwater convection in a permeable 3-4 km radial fracture zone transecting the entire flank of the volcano. This focuses heat and fluid flux and can explain the three distinct fumarole zones located along the fracture. We hypothesize that the rapid response of fumarole temperature to volcanic activity is due to increased flow of gas through the vadose zone, possibly caused by changes in the subsurface pressure distribution. Numerical models show that an abrupt injection of hot gas, at approximately 100 times background rates, can cause the rapid increase in temperature observed at the fumaroles during volcanic activity. A decrease in hot fluid injection rate can explain the gradual decrease in temperature afterwards. Mixing with surrounding vadose-zone fluids can result in the consistent and abrupt decreases in temperature to background level following hot gas injection. Fumaroles result from complex interaction of the volcanic-hydrologic-geologic systems, and can therefore provide insight into these systems. Increases in fumarole temperature correspond to increased gas flux related to changes in volcanic activity, suggesting that monitoring of distal fumaroles has potential as a volcano monitoring tool, and that fumarole temperatures can provide insight into the response of shallow gas systems to volcanic activity.

Mudanças de uso e manejo influenciam o acúmulo de carbono (C) no solo e o fluxo de gases do efeito estufa (GEE). No Brasil, sobretudo nos biomas Amazônia e Cerrado, historicamente vegetações nativas são convertidas em pastagens e agricultura emitindo consideráveis quantidades de GEE para a atmosfera. Áreas sob pastagens e agricultura vêm sendo convertidas em sistemas mais intensificados e tecnicamente mais avançados, tais como os sistemas de integração lavoura-pecuária (ILP), os quais têm a capacidade de acumular C no solo e mitigar as emissões de GEE para atmosfera. O objetivo deste estudo foi avaliar as modificações nos estoques de C do solo e nos fluxos de GEE em áreas sob mudança de uso da terra nos biomas Amazônia e Cerrado. Foram avaliadas áreas sob vegetação nativa, pastagens, sucessão de cultivos e ILP em diferentes condições edafoclimáticas. O manejo da fertilidade do solo sob pastagem afeta produção de biomassa, que por sua vez influencia o acúmulo ou perda de C. Pastagem cultivada em solo fértil acumulou 0,46 Mg de C ha-1 ano-1. Sob baixa fertilidade natural, obsrvou-se perdas de 0,15 e 1,53 Mg de C ha-1 ano-1, respectivamente para pastagem não degradada e degradada. A conversão de vegetação nativa e pastagem para agricultura, mesmo cultivada sob SPD, reduziu o estoque de C, exibindo perdas de 0,69 a 1,44 Mg ha-1 ano-1. A implantação de sistemas de ILP em áreas sob sucessão de cultivos aumentou os estoques de C no solo, com taxas varaindo de 0,82 a 2,58 Mg ha-1 ano-1. Aplicando a modelagem matemática, com o modelo Century, verificou-se as mesmas tendências de acúmulo ou perdas de C no solo. Entretanto, o modelo subestimou os estoques de C em todas as áreas avaliadas. Em Montividiu, a avalaição do fluxo de GEE em diferentes usos e manejos da terra, evidenciou maior emissão CCO2 na pastagem (10820 kg ha-1) e esta foi significativamente maior em relação à sucessão de cultivos (4987 kg ha-1) e ILP (6565 kg ha-1). Emissão de N-N2O foi maior em ILP (2,00 kg ha-1 ano-1) e menor na vegetação nativa (0,35 kg ha-1 ano-1). Os fluxos de C-CH4 resultaram em emissão de 1,67 kg ha-1 ano-1 na pastagem e em absorção nas demais áreas. Em ILP, os manejos aplicados à soqueira do algodoeiro, resultaram em diferenças nos fluxos de GEE. O manejo químico, sem perturbação do solo, reduziu a emissão de CO2, aumentou a emissão de N2O e não influenciou os fluxos de CH4. Utilizando as taxas de acúmulos de C e os fluxos de GEE obteve-se o seqüestro de C no solo. As taxas de seqüestro, expressas em C equivalente, evidenciaram perdas da ordem de 0,43 e 0,77 Mg ha-1 ano-1, respectivamente para a conversão de Cerrado para pastagem e sucessão de cultivos. Implantação de ILP em áreas sob sucessão de cultivos resultou em seqüestro de C pelo solo, independente do manejo aplicado. Manejo químico seqüestrou 1,05 Mg de C ha-1 ano-1. Manejo mecânico com o equipamento Cotton 1000 e grade aradora seqüestraram 0,58 e 0,71 Mg de C ha-1 ano-1, respectivamente. A implantação de sistemas ILP se mostrou uma excelente alternativa para acumular C no solo e mitigar as emissões de GEE para atmosfera. / Changes on land use and management influence the accumulation of carbon (C) in soil and the greenhouse gas (GHG) fluxes. In Brazil, especially in Amazonia and Cerrados biomes, the native vegetation has been historically converted in pastures and agriculture causing considerable amount of GHG emissions to the atmosphere. Recently, pastures and agricultural activities have been adopting more intensified and technically advanced land management systems, such as the integrated crop-livestock (ICL) system, which has the capacity to increase soil C accumulation and promote GHG mitigation. The objective of this study was to evaluate the alterations in soil C stock and GHG fluxes in areas under land use changes in the Amazonia and Cerrados biomes. The study focused on areas under native vegetation, pasture, crop succession and ICL under different edaphoclimatic conditions. The fertility management of soil under pasture affects the biomass production which, in turn, influences not only the soil C accumulation but also the C loss. This study showed that pasture cultivated in fertile soil presented an accumulation of 0.46 Mg of C ha-1 year-1. Under naturally low soil fertility, losses of 0.15 and 1.53 Mg of C ha-1 year -1 were observed in non-degraded and degraded pastures, respectively. Conversion of native vegetation and pasture to agriculture, even when cultivated under no-tillage, caused the reduction of C stock and showed losses from 0.69 to 1.44 Mg ha-1 year -1. The implementation of ICL systems in crop succession areas caused the increase of soil C stock with rates ranging from 0.82 to 2.58 Mg ha-1 year -1. By applying the Century model, the same tendencies in soil C accumulation and C loss were observed. However, the model underestimated the C stock in all areas under evaluation. In Montividiu, Goiás State, the evaluation of GHG fluxes from different land uses and management showed that pasture produced higher C-CO2 emissions (10829 kg ha-1 year -1) than crop succession (4987 kg ha-1 year -1) and ICL (6565 kg ha- 1 year -1). The N-N2O emission was higher from ICL (2.00 kg ha-1 year-1) and lower from native vegetation (0.35 kg ha-1 year-1). Regarding the C-CH4 emissions from pastures, the fluxes were in the order of 1.67 kg ha-1year-1 while the other areas showed sink. In ICL, the soil management applied to the cotton stalk resulted in GHG flux differences. Chemical management with no soil disturbance reduced the CO2 emissions, increased N2O emissions and showed no influence on CH4 fluxes. Carbon sequestration rates, expressed in C equivalent, showed losses in the order of 0.43 and 0.77 Mg ha-1 year-1, respectively, from the conversion of Cerrado to pasture and crop succession. The implementation of ICL in areas under crop succession resulted in C sequestration in soil, regardless the type of management applied. Chemical management produced C sequestration of 1.05 Mg ha-1 year -1. Mechanical management with Cotton 1000 equipment and full tillage produced the sequestration of 0.58 and 0.71 Mg of C ha-1 year-1, respectively. The implementation of ICL systems showed to be an excellent alternative for soil C accumulation and mitigation of GHG emission.