Microscale Processes and Dynamics during CH4–CO2 GuestMolecule Exchange in Gas Hydrates

The exchange of CH4 by CO2 in gas hydrates is of interest for the production of natural gas from methane hydrate with net zero climate gas balance, and for managing risks that are related to sediment destabilization and mobilization after gas-hydrate dissociation. Several experimental studies on the dynamics and efficiency of the process exist, but the results seem to be partly inconsistent. We used confocal Raman spectroscopy to map an area of several tens to hundreds µm of a CH4 hydrate sample during its exposure to liquid and gaseous CO2. On this scale, we could identify and follow different processes in the sample that occur in parallel. Next to guest-molecule exchange, gas-hydrate dissociation also contributes to the release of CH4. During our examination period, about 50% of the CO2 was bound by exchange for CH4 molecules, while the other half was bound by new formation of CO2 hydrates. We evaluated single gas-hydrate grains with confirmed gas exchange and applied a diffusion equation to quantify the process. Obtained diffusion coefficients are in the range of 10−13–10−18 m2/s. We propose to use this analytical diffusion equation for a simple and robust modeling of CH4 production by guest-molecule exchange and to combine it with an additional term for gas-hydrate dissociation.

Effect of Paddy-Upland Rotation System on the Net Greenhouse Gas Balance as the Sum of Methane and Nitrous Oxide Emissions and Soil Carbon Storage: A Case in Western Japan

To investigate the effect of paddy-upland (PU) rotation system on greenhouse gas emissions, methane (CH4) and nitrous oxide (N2O) emissions were monitored for three years for a PU rotation field (four cultivations (wheat-soybean-rice-rice) over three years) and continuous paddy (CP) field on alluvial soil in western Japan. Soil carbon storage was also calculated using an improved Rothamsted Carbon (RothC) model. The net greenhouse gas balance was finally evaluated as the sum of CO2eq of the CH4, N2O and changes in soil carbon storage. The average CH4 emissions were significantly lower and the average N2O emissions were significantly higher in the PU field than those in the CP field (p < 0.01). On CO2 equivalent basis, CH4 emissions were much higher than N2O emission. In total, the average CO2eq emissions of CH4 plus N2O in the PU field (1.81 Mg CO2 ha−1 year−1) were significantly lower than those in the CP field (7.42 Mg CO2 ha−1 year−1) (p < 0.01). The RothC model revealed that the changes in soil carbon storage corresponded to CO2eq emissions of 0.57 and 0.09 Mg CO2 ha−1 year−1 in the both fields, respectively. Consequently, the net greenhouse gas balance in the PU and CP fields were estimated to be 2.38 and 7.51 Mg CO2 ha−1 year−1, respectively, suggesting a 68% reduction in the PU system. In conclusion, PU rotation system can be regarded as one type of the climate-smart soil management.