Analysis of crystal growth of methane hydrate using molecular dynamics simulation

Methane hydrate is a crystalline compound with methane molecules enclosed in cages formed by hydrogen-bonded water molecules. Understanding the mechanism of nucleation and crystal growth from methane vapour and liquid water is important for all hydrate applications. However, processes near the water/methane interface are still unclear. In this work, we focused on the crystal growth of methane hydrate seeds located near the water/methane interface. We performed molecular dynamics (MD) simulation and analysed the crystal growth of the hydrate seed at the interface. New cages formed in the liquid water phase were stabilised when they shared faces with the hydrate seed. We also investigated the crystal growth rate as the time development of the number of methane molecules trapped in hydrate cages, based on the trajectory of the MD simulation. The calculated growth rate in the direction that covers the interface was 1.38 times that in the direction towards the inside of the water phase.     

CO<Subscript>2</Subscript> enrichment affects eco-physiological growth of maize and alfalfa under different water stress regimes in the UAE

Water stress has been reported to alter morphology and physiology of plants affecting chlorophyll content, stomatal size and density. In this study, drought stress mitigating effects of CO₂ enrichment was assessed in greenhouse conditions in the hot climate of UAE. Commercially purchased maize (Zea mays L.) and alfalfa (Medicago sativa L.) were seeded in three different custom-built cage structures, inside a greenhouse. One cage was kept at 1000 ppm CO₂, the second at 700 ppm CO₂, and the third at ambient greenhouse CO₂ environment (i.e. 435 ppm). Three water stress treatments HWS (200 ml per week), MWS (400 ml per week), and CWS (600 ml per week) were given to each cage so that five maize pots and five alfalfa pots in each cage received same water stress treatments. In maize, total chlorophyll content was similar or higher in water stress treatments compared to control for all CO₂ concentrations. Stomatal lengths were higher in enriched CO₂ environments under water stress. At 700 ppm CO₂, stomatal widths decreased as water stress increased from MWS to HWS. At both enriched CO₂ environments, stomatal densities decreased compared to ambient CO₂ environment. In alfalfa, there was no significant increase in total chlorophyll content under enriched CO₂ environments, even though a slight increase was noticed.     

Partitioning pathways of CO2 production in peatlands with stable carbon isotopes

Although methanogenic pathways generally produce equimolar amounts of carbon dioxide and methane, CO₂ concentrations are often reported to be higher than CH₄ concentrations in both field and laboratory incubation studies of peat decomposition. In field settings, higher pore water concentrations of CO₂ may result from the loss of methane by: (1) ebullition due to the low solubility of methane in pore water and (2) vascular-plant transport. Higher CO₂ concentrations may also be caused by: (1) production of additional CO₂ by high-molecular weight (HMW) organic matter (OM) fermentation and/or (2) respiration from non-methanogenic pathways. In this study of a peatland where advection and transverse dispersion were the dominant pore water solute transport mechanisms, an isotope-mass balance approach was used to determine the proportions of CO₂ formed from non-fractionating OM respiration and HMW fermentation relative to CO₂ production from methanogenesis. This approach also allowed us to estimate the loss of CH₄ from the belowground system. The pathways of CO₂ production varied with depth and surface vegetation type. In a Carex-dominated fen, methane production initially produced 40 % of the total CO₂ and then increased to 90–100 % with increasing depth. In a Sphagnum-dominated bog, methanogenesis resulted in 60 % of total CO₂ production which increased to 100 % at depth. Both bogs and fens showed 85–100 % of methane loss from pore waters. Our results indicate that the isotopic composition of dissolved CO₂ is a powerful indicator to allow partitioning of the processes affecting peat remineralization and methane production.     

Monte Carlo study of sI hydrogen hydrates

In this study, we perform grand canonical Monte Carlo simulations to evaluate the hydrogen storage capacity of structure I (sI) hydrogen hydrates at pressures up to 500 MPa. Initially, we calculate the upper limit of H₂ content of sI hydrates by studying the hypothetical sI hydrate, where H₂ is the single guest component. It is found that the storage capacity of the hypothetical pure H₂ sI hydrate could reach 3.5 wt% at 500 MPa and 274 K. Depending on pressure, the large cavities of the pure H₂ hydrate can accommodate up to three H₂ molecules while the small ones are singly occupied at most, even at pressures as high as 500 MPa, without any double occupancy being observed. Subsequently, the binary H₂–ethylene oxide (EO) hydrate is examined. In this case, the large cavities are occupied by a single EO molecule while the small cavities can accommodate at most a single H₂ molecule. Such configuration results in a maximum H₂ content of only 0.37 wt%. The hydrogen storage capacity does not improve significantly even in case when EO is replaced by a component with smaller molecular weight.     

Analysis of dissociation process for gas hydrates by molecular dynamics simulation

The dissociation processes of methane and carbon dioxide hydrates were investigated by molecular dynamics simulation. The simulations were performed with 368 water molecules and 64 gas molecules using NPT ensembles. The TraPPE (single-site) and 5-site models were adopted for methane molecules. The EPM2 (3-site) and SPC/E models were used for carbon dioxide and water molecules, respectively. The simulations were carried out at 270 K and 5.0 MPa for hydrate stabilisation. Then, temperature was increased up to 370 K. The temperature increasing rates were 0.1–20 TK/s. The gas hydrates dissociated during increasing temperature or at 370 K. The potential models of methane molecule did not much influence the dissociation process of methane hydrate. The mechanisms of dissociation process were analysed with the coordination numbers and mean square displacements. It was found that the water cages break down first, then the gas molecules escape from the water cages. The methane hydrate was more stable than the carbon dioxide hydrate at the calculated conditions.     

Molecular simulation of cage occupancy and selectivity of binary THF–H2 sII hydrate

The hydrogen capacity of the binary THF–H₂ sII hydrate is determined by the cage occupancy and by the selectivity of guest molecules. Grand canonical Monte Carlo (GCMC) simulation is used to study the cage occupancy and selectivity of guest molecules from the equilibrium configuration of the binary sII hydrate. The cage framework is regarded as a rigid body and the number of guest molecules is varied to preserve the grand canonical ensemble. The occupancy and selectivity were investigated at a temperature of 270 K for pressures ranging from 0.1 to 200 MPa. It was found that most large cages select THF as guest molecules while small cages include only hydrogen molecules. Multiple occupancy of hydrogen, up to four molecules in large cages and two molecules in small cages, was found as the pressure increases. GCMC results show that the hydrogen capacity is approximately 1.1 wt% at 200 MPa.     

Carbon dioxide and methane emissions from interfluvial wetlands in the upper Negro River basin, Brazil

Extensive interfluvial wetlands occur in the upper Negro River basin (Brazil) and contain a mosaic of vegetation dominated by emergent grasses and sedges with patches of shrubs and palms. To characterize the release of carbon dioxide and methane from these habitats, diffusive and ebullitive emissions and transport through plant aerenchyma were measured monthly during 2005 in permanently and seasonally flooded areas. CO₂ emissions averaged 2193 mg C m^?2 day^?1. Methane was consumed in unflooded environments and emitted in flooded environments with average values of ?4.8 and 60 mg C m^?2 day^?1, respectively. Bubbles were emitted primarily during falling water periods when hydrostatic pressure at the sediment?Cwater interface declined. CO₂ and CH₄ emissions increased when dissolved O₂ decreased and vegetation was more abundant. Total area and seasonally varying flooded areas for two wetlands, located north and south of the Negro River, were determined through analysis of synthetic aperture radar and optical remotely sensed data. The combined areas of these two wetlands (3000 km²) emitted 1147 Gg C year^?1 as CO₂ and 31 Gg C year^?1 as CH₄. If these rates are extrapolated to the area occupied by hydromorphic soils in the upper Negro basin, 63 Tg C year^?1 of CO₂ and 1.7 Tg C year^?1 as CH₄ are estimated as the regional evasion to the atmosphere.     

Biogeochemistry of organic carbon, CO2, CH4, and trace elements in thermokarst water bodies in discontinuous permafrost zones of Western Siberia

Active processes of permafrost thaw in Western Siberia increase the number of soil subsidencies, thermokarst lakes and thaw ponds. In continuous permafrost zones, this process promotes soil carbon mobilisation to water reservoirs, as well as organic matter (OM) biodegradation, which produces a permanent flux of carbon dioxide (CO₂) to the atmosphere. At the same time, the biogeochemical evolution of aquatic ecosystems situated in the transition zone between continuous permafrost and permafrost-free terrain remains poorly known. In order to better understand the biogeochemical processes that occur in thaw ponds and lakes located in discontinuous permafrost zones, we studied ~30 small (1–100,000 m²) shallow (<1 m depth) lakes and ponds formed as a result of permafrost subsidence and thaw of the palsa bog located in the transition zone between the tundra and forest-tundra (central part of Western Siberia). There is a significant increase in dissolved CO₂ and methane (CH₄) concentration with decreasing water body surface area, with the largest supersaturation with respect to atmospheric CO₂ and CH₄ in small (<100 m²) permafrost depressions filled with thaw water. Dissolved organic carbon (DOC), conductivity, and metal concentrations also progressively increase from large lakes to thaw ponds and depressions. As such, small water bodies with surface areas of 1–100 m² that are not accounted for in the existing lake and pond databases may significantly contribute to CO₂ and CH₄ fluxes to the atmosphere, as well as to the stocks of dissolved trace elements and organic carbon. In situ lake water incubation experiments yielded negligible primary productivity but significant oxygen consumption linked to the mineralisation rate of dissolved OM by heterotrophic bacterioplankton, which produce a net CO₂ flux to the atmosphere of 5 ± 2.5 mol C m² year^?1. The most significant result of this study, which has long-term consequences on our prediction of aquatic ecosystem development in the course of permafrost degradation is CO₂, CH₄, and DOC concentrations increase with decreasing lake age and size. As a consequence, upon future permafrost thaw, the increase in the number of small water bodies, accompanied by the drainage of large thermokarst lakes to the hydrological network, will likely favour (i) the increase of DOC and colloidal metal stocks in surface aquatic systems, and (ii) the enhancement of CO₂ and CH₄ fluxes from the water surface to the atmosphere. According to a conservative estimation that considers that the total area occupied by water bodies in Western Siberia will not change, this increase in stocks and fluxes could be as high as a factor of ten.     

Carbon cycling within the sulfate-methane-transition-zone in marine sediments from the Ulleung Basin

The significance of the various carbon cycling pathways in driving the sharp sulfate methane transition zone (SMTZ) observed at many locations along continental margins is still a topic of debate. Unraveling these processes is important to our understanding of the carbon cycle in general and to evaluate whether the location of this front can be used to infer present and past methane fluxes from deep reservoirs (e.g., gas hydrate). Here we report the pore water data from the second Ulleung Basin Gas Hydrate Expedition and on the results of a box model that balances solute fluxes among different carbon pools and satisfies the observed isotopic signatures. Our analysis identifies a secondary methanogenesis pathway within the SMTZ, whereby 25–35 % of the dissolved inorganic carbon (DIC) produced by the anaerobic oxidation of methane (AOM) is consumed by CO₂ reduction (CR). To balance this DIC consumption, a comparable rate of organic matter degradation becomes necessary, which in turn consumes a significant amount of sulfate. The fraction of sulfate consumed by AOM ranges from 70 to 90 %. Whereas a simple mass balance would suggest a one to one relationship between sulfate and methane fluxes; our isotopic considerations show that methane flux estimates based solely on sulfate data may be in error by as much as 30 %. Furthermore, the carbon cycling within the SMTZ is fueled by a significant contribution (10–40 %) of methane produced by CR just below the SMTZ. Therefore sulfate gradient cannot necessarily be used to infer methane contributions from gas hydrate reservoirs that may lay tens to hundreds of meters below the SMTZ.     

Influence of weather variables on methane and carbon dioxide flux from a shallow pond

Freshwaters are important sources of the greenhouse gases methane (CH₄) and carbon dioxide (CO₂) to the atmosphere. Knowledge about temporal variability in these fluxes is very limited, yet critical for proper study design and evaluating flux data. Further, to understand the reasons for the variability and allow predictive modeling, the temporal variability has to be related to relevant environmental variables. Here we analyzed the effect of weather variables on CH₄ and CO₂ flux from a small shallow pond during a period of 4 months. Mean CH₄ flux and surface water CH₄ concentration were 8.0 [3.3–15.1] ± 3.1 mmol m^?2 day^?1 (mean [range] ± 1 SD) and 1.3 [0.3–3.5] ± 0.9 µM respectively. Mean CO₂ flux was 1.1 [?9.8 to 16.0] ± 6.9 mmol m^?2 day^?1. Substantial diel changes in CO₂ flux and surface water CH₄ concentration were observed during detailed measurements over a 24 h cycle. Thus diel patterns need to be accounted for in future measurements. Significant positive correlations of CH₄ emissions with temperature were found and could include both direct temperature effects as well as indirect effects (e.g. related to the growth season and macrophyte primary productivity providing organic substrates). CO₂ flux on the other hand was negatively correlated to temperature and solar radiation, presumably because CO₂ consumption by plants was higher relative to CO₂ production by respiration during warm sunny days. Interestingly, CH₄ fluxes were comparable to ponds with similar morphometry and macrophyte abundance in the tropics. We therefore hypothesize that CH₄ and CO₂ summer emissions from ponds could be more related to the morphometry and dominating primary producers rather than latitude per se. Data indicate that CH₄ emissions, given the system characteristic frameworks, is positively affected by increased temperatures or prolonged growth seasons.     

Decomposition of CH4 hydrate: effects of temperature and salt from molecular simulations

We report a molecular simulation study to investigate the decomposition of CH₄ hydrate. The decomposition is revealed to be stepwise from the outer to inner layers. Upon decomposition, the number of 5¹²6² cages drops faster than that of 5¹² cages. CH₄ molecules are released, dissolved in water, then enter gas phase; meanwhile, CH₄ bubbles may form particularly at a high temperature. Based on the variations of potential energy, order parameter, cage number and density profile of CH₄ at different temperatures (300, 330, 345 and 360 K) and NaCl concentrations (0, 0.6 and 1.8 M), the effects of temperature and salt are comprehensively examined. With increasing temperature, the decomposition in pure water is accelerated, whereas two opposite effects are observed in NaCl solution. At 330 K, the decomposition is retarded at a higher NaCl concentration, as attributed to the reduced CH₄ solubility in NaCl solution and the participation of ions in cage formation; at 360 K, however, the decomposition is accelerated when NaCl concentration increases due to bubble formation. This simulation study provides microscopic insights into hydrate decomposition, which might be useful towards the optimisation of operating conditions for CH₄ production from CH₄ hydrate.     

Application of Gibbs Ensemble and NPT Monte Carlo Simulation to the Development of Improved Processes for H2S-rich Gases

The design of improved processes for producing hydrogen sulphide (H₂S)-rich natural gases faces a general scarcity of experimental data, because of the high toxicity and corrosive character of H₂S. We present here a prospective application of Monte Carlo simulation to predict desired fluid properties.

A first step was the selection of intermolecular potentials for water, H₂S, carbon dioxide (CO₂) and methane on the basis of pure component properties (vapour pressures, vapourisation enthalpies, liquid densities, supercritical densities at high pressure). A second step involved the prediction of phase diagrams of binary and ternary mixtures of the methane–H₂S–water system, using two-phase and three-phase Gibbs ensemble simulations. In a third step the density and excess enthalpy of the CO₂–H₂S system were computed for a large range of pressure, temperature and compositions.

Comparison with available experimental data showed that all investigated properties could be consistently predicted without needing parameter calibration on binary data. The results also provided a qualitative understanding of water solubility in H₂S-rich fluids based on molecular self-association.     

Anaerobic degradation of phenol in sewage sludge

Summary Anaerobic phenol degrading consortia were selected in sewage sludge and culture conditions were improved to allow maximum degradation rates of 0.9 g/l·d. Phenol had to be added in two portions of 0.45 g/l at intervals of 12 h to keep the fermentation at stable conditions. From U-¹⁴C-phenol little benzoate and acetate were formed as intermediates under a N₂:CO₂ gas phase. Final products were methane and CO₂. When methanogenesis was inhibited by BESA, less labeled methane and CO₂ were formed and labeled acetate remained undegraded. Turnover rates of phenol were significantly reduced in the presence of a H₂:CO₂ gas atmosphere and benzoate was formed from phenol and CO₂. Acetate did not accumulate remarkably. After the H₂:CO₂ was converted to methane or was exchanged by N₂:CO₂ the accumulated benzoate was further degraded to methane and CO₂. Elevated pools of acetate in sewage sludge led also to a reduction of the phenol degradation rates and presumably to an increased concentration of benzoate. In fresh sewage sludge benzoate degradation proceeds immediately, while the degradation of phenol starts only after a lag-phase of 3–10 days.     

A three-dimensional model of CO2 transport in airspaces and mesophyll cells of a silver birch leaf

A realistic numerical three‐dimensional (3D) model was constructed to study CO₂ transport inside a birch leaf. The model included chloroplasts, palisade and spongy mesophyll cells, airspaces, stomatal opening and the leaf boundary layer. Diffusion equations for CO₂ were solved for liquid(mesophyll) and gaseous(air) phases. Simulations were made in typical ambient field conditions varying stomatal opening, photosynthetic capacity and temperature. Doubled ambient CO₂ concentration was also considered. Changes in variables caused non‐linear effects in the total flux, especially when compared with the results of double CO₂ concentration. The reduction in stomatal opening size had a smaller effect on the total flux in doubled concentrations than ambient CO₂. The reduced photosynthetic capacity had a similar effect on the flux in both cases. The palisade and spongy mesophyll cells had unequal roles mainly due to the light absorption profile. Results from the 3D simulation were also compared to the classical one‐dimensional resistance approach. Liquid and gas phase resistances were estimated and found strongly variable according to changes in temperature and degree of stomatal opening. For the birch leaves modelled, intercellular airspace resistance was small (2% of the total resistance in saturating irradiance conditions at 25 °C at stomatal opening diameter of 4 µm) whereas the liquid phase resistance was significant (23% for mesophyll and chloroplasts in the same ‘base case’). The absorption of CO₂ into water at cell surfaces caused additional (strongly temperature dependent) resistance which accounted for 36% of the total resistance in the base case.     

Gaseous and fluvial carbon export from an Amazon forest watershed

The transfer of carbon (C) from Amazon forests to aquatic ecosystems as CO₂ supersaturated in groundwater that outgases to the atmosphere after it reaches small streams has been postulated to be an important component of terrestrial ecosystem C budgets. We measured C losses as soil respiration and methane (CH₄) flux, direct CO₂ and CH₄ fluxes from the stream surface and fluvial export of dissolved inorganic C (DIC), dissolved organic C (DOC), and particulate C over an annual hydrologic cycle from a 1,319-ha forested Amazon perennial first-order headwater watershed at Tanguro Ranch in the southern Amazon state of Mato Grosso. Stream pCO₂ concentrations ranged from 6,491 to 14,976 ??atm and directly-measured stream CO₂ outgassing flux was 5,994 ± 677 g C m^?2 y^?1 of stream surface. Stream pCH₄ concentrations ranged from 291 to 438 ??atm and measured stream CH₄ outgassing flux was 987 ± 221 g C m^?2 y^?1. Despite high flux rates from the stream surface, the small area of stream itself (970 m², or 0.007% of watershed area) led to small directly-measured annual fluxes of CO₂ (0.44 ± 0.05 g C m² y^?1) and CH₄ (0.07 ± 0.02 g C m² y^?1) per unit watershed land area. Measured fluvial export of DIC (0.78 ± 0.04 g C m^?2 y^?1), DOC (0.16 ± 0.03 g C m^?2 y^?1) and coarse plus fine particulate C (0.001 ± 0.001 g C m^?2 y^?1) per unit watershed land area were also small. However, stream discharge accounted for only 12% of the modeled annual watershed water output because deep groundwater flows dominated total runoff from the watershed. When C in this bypassing groundwater was included, total watershed export was 10.83 g C m^?2 y^?1 as CO₂ outgassing, 11.29 g C m^?2 y^?1 as fluvial DIC and 0.64 g C m^?2 y^?1 as fluvial DOC. Outgassing fluxes were somewhat lower than the 40?C50 g C m^?2 y^?1 reported from other Amazon watersheds and may result in part from lower annual rainfall at Tanguro. Total stream-associated gaseous C losses were two orders of magnitude less than soil respiration (696 ± 147 g C m^?2 y^?1), but total losses of C transported by water comprised up to about 20% of the ± 150 g C m^?2 (±1.5 Mg C ha^?1) that is exchanged annually across Amazon tropical forest canopies.     

Structural and dynamical properties predicted by reactive force fields simulations for four common pure fluids at liquid and gaseous non-reactive conditions

Four common pure fluids were chosen to elucidate the reliability of reactive force fields in estimating bulk properties of selected molecular systems: CH₄, H₂O, CO₂ and H₂. The pure fluids are not expected to undergo chemical reactions at the conditions chosen for these simulations. The ‘combustion’ ReaxFF was chosen as reactive force field. In the case of water, we also considered the ‘aqueous’ ReaxFF model. The results were compared to data obtained implementing popular classic force fields. In the gas phase, it was found that simulations conducted using the ‘combustion’ ReaxFF formalism yield structural properties in reasonable good agreement with classic simulations for CO₂ and H₂, but not for CH₄ and H₂O. In the liquid phase, ‘combustion’ ReaxFF simulations reproduce reasonably well the structure obtained from classic simulations for CH₄, degrade for CO₂ and H₂, and are rather poor for H₂O. In the gas phase, the simulation results are compared to experimental second virial coefficient data. The ‘combustion’ ReaxFF simulations yield second virial coefficients that are not sufficiently negative for CH₄ and CO₂, and slightly too negative for H₂. The ‘combustion’ ReaxFF parameterisation induces too strong an effective attraction between water molecules, while the ‘aqueous’ ReaxFF yields a second virial coefficient that is in reasonable agreement with experiments. The ‘combustion’ ReaxFF parameterisation yields acceptable self-diffusion coefficients for gas-phase properties of CH₄, CO₂ and H₂. In the liquid phase, the results are good for CO₂, while the self-diffusion coefficient predicted for liquid CH₄ is slower, and that predicted for liquid H₂ is about nine times faster than those expected based on classic simulations. The ‘aqueous’ ReaxFF parameterisation yields good results for both the structure and the diffusion of both liquid and vapour water.     

Nitrous oxide and methane exchange in two small temperate forest catchments—effects of hydrological gradients and implications for global warming potentials of forest soils

The magnitude of greenhouse gas (GHG) flux rates may be important in wet and intermediate wet forest soils, but published estimates are scarce. We studied the surface exchange of methane (CH₄) and nitrous oxide (N₂O) from soil along toposequences in two temperate deciduous forest catchments: Strødam and Vestskoven. The soil water regime ranged from fully saturated to aerated within the catchments. At Strødam the largest mean flux rates of N₂O (15 μg N₂O-N m^?2 h^?1) were measured at volumetric soil water contents (SWC) between 40 and 60% and associated with low soil pH compared to smaller mean flux rates of 0-5 μg N₂O-N m^?2 h^?1 for drier (SWC < 40%) and wet conditions (SWC > 80%). At Vestskoven the same response of N₂O to soil water content was observed. Average CH₄ flux rates were highly variable along the toposequences (?17 to 536 μg CH₄-C m^?2 h^?1) but emissions were only observed above soil water content of 45%. Scaled flux rates of both GHGs to catchment level resulted in emission of 322 and 211 kg CO₂-equivalents ha^?1 year^?1 for Strødam and Vestskoven, respectively, with N₂O contributing the most at both sites. Although the wet and intermediate wet forest soils occupied less than half the catchment area at both sites, the global warming potential (GWP) derived from N₂O and CH₄ was more than doubled when accounting for these wet areas in the catchments. The results stress the importance of wet soils in assessments of forest soil global warming potentials, as even small proportions of wet soils contributes substantially to the emissions of N₂O and CH₄.     

Release of CO2 and CH4 from lakes and drainage ditches in temperate wetlands

Shallow fresh water bodies in peat areas are important contributors to greenhouse gas fluxes to the atmosphere. In this study we determined the magnitude of CH₄ and CO₂ fluxes from 12 water bodies in Dutch wetlands during the summer season and studied the factors that might regulate emissions of CH₄ and CO₂ from these lakes and ditches. The lakes and ditches acted as CO₂ and CH₄ sources of emissions to the atmosphere; the fluxes from the ditches were significantly larger than the fluxes from the lakes. The mean greenhouse gas flux from ditches and lakes amounted to 129.1 ± 8.2 (mean ± SE) and 61.5 ± 7.1 mg m^?2 h^?1 for CO₂ and 33.7 ± 9.3 and 3.9 ± 1.6 mg m^?2 h^?1 for CH₄, respectively. In most water bodies CH₄ was the dominant greenhouse gas in terms of warming potential. Trophic status of the water and the sediment was an important factor regulating emissions. By using multiple linear regression 87% of the variation in CH₄ could be explained by PO₄ ^3? concentration in the sediment and Fe²⁺ concentration in the water, and 89% of the CO₂ flux could be explained by depth, EC and pH of the water. Decreasing the nutrient loads and input of organic substrates to ditches and lakes by for example reducing application of fertilizers and manure within the catchments and decreasing upward seepage of nutrient rich water from the surrounding area will likely reduce summer emissions of CO₂ and CH₄ from these water bodies.     

Seasonal variability of methane in the rivers and lagoons of Ivory Coast (West Africa)

We report a data-set of dissolved methane (CH₄) in three rivers (Comoé, Bia and Tanoé) and five lagoons (Grand-Lahou, Ebrié, Potou, Aby and Tendo) of Ivory Coast (West Africa), during the four main climatic seasons (high dry season, high rainy season, low dry season and low rainy season). The surface waters of the three rivers were over-saturated in CH₄ with respect to atmospheric equilibrium (2221–38719%), and the seasonal variability of CH₄ seemed to be largely controlled by dilution during the flooding period. The strong correlation of CH₄ concentrations with the partial pressure of CO₂ (pCO₂) and dissolved silicate (DSi) confirm the dominance of a continental sources (from soils) for both CO₂ and CH₄ in these rivers. Diffusive air–water CH₄ fluxes ranged between 25 and 1187 μmol m^?2 day^?1, and annual integrated values were 288 ± 107, 155 ± 38, and 241 ± 91 μmol m^?2 day^?1 in the Comoé, Bia and Tanoé rivers, respectively. In the five lagoons, surface waters were also over-saturated in CH₄ (ranging from 1496 to 51843%). Diffusive air–water CH₄ fluxes ranged between 20 and 2403 μmol m^?2 day^?1, and annual integrated values were 78 ± 34, 338 ± 217, 227 ± 79, 330 ± 153 and 326 ± 181 μmol m^?2 day^?1 in the Grand-Lahou, Ebrié, Potou, Aby and Tendo lagoons, respectively. The largest CH₄ over-saturations were observed in the Tendo and Aby lagoons that are permanently stratified systems (unlike the other three lagoons), leading to anoxic bottom waters favorable for a large CH₄ production. In addition, these two stratified lagoons showed low pCO₂ values due to high primary production, which suggests an efficient transfer of organic matter across the pycnocline. As a result, the stratified Tendo and Aby lagoons were respectively, a low source of CO₂ to the atmosphere and a sink of atmospheric CO₂ while the other three well-mixed lagoons were strong sources of CO₂ to the atmosphere but less over-saturated in CH₄.