Methane Dynamics Research Articles

Counteractions between biotic and abiotic factors on methane dynamics in a boreal peatland: Vegetation composition change vs warming and nitrogen deposition

Methane (CH4) fluxes in boreal peatlands are vulnerable to global change, including climate warming, elevated nitrogen (N) deposition, and vegetation composition change. However, few studies focus on the interactions of these factors, particularly combining all of them, which leads to a large degree of uncertainty in predicting CH4 emissions from peatlands in the future. In this study, experimental warming, N addition, and vegetation composition change were conducted for five years at a boreal peatland in western Newfoundland, Canada. We found that graminoid absence substantially decreased CH4 emissions by 72% owing to the reduction of root exudates for CH4 production and aerenchyma for CH4 transport; however, this negative effect disappeared under the combination of warming and N addition, which can be attributed to the elevated temperature sensitivity of CH4. Additionally, we observed that vegetation productivity was the main control when the graminoid was present, but not the major control when the shrub was present only, suggesting the proper parameters should be selected under different vegetation compositions so as to accurately project CH4 emissions in the context of climate change. Compared with the studies focusing on one or two environmental changes, this experiment is valuable for providing empirical evidence on the parameterization of CH4 fluxes in the biogeochemical model of boreal peatlands and in the global coupled climate-carbon model.

Continuous Dynamics of Dissolved Methane Over 2 Years and its Carbon Isotopes (δ13C, Δ14C) in a Small Arctic Lake in the Mackenzie Delta

AbstractSeasonally ice‐covered permafrost lakes in the Arctic emit methane to the atmosphere during periods of open‐water. However, processes contributing to methane cycling under‐ice have not been thoroughly addressed despite the potential for significant methane emission to the atmosphere at ice‐out. We studied annual dissolved methane dynamics within a small (0.2 ha) Mackenzie River Delta lake using sensor and water sampling packages that autonomously and continuously collected lake water samples, respectively, for two years at multiple water column depths. Lake physical and biogeochemical properties (temperature; light; concentrations of dissolved oxygen, manganese, iron, and dissolved methane, including stable carbon, and radiocarbon isotopes) revealed annual patterns. Dissolved methane concentrations increase under‐ice after electron acceptors (oxygen, manganese, and iron oxides) are depleted or inaccessible from the water column. The radiocarbon age of dissolved methane suggests a source from recently decomposed carbon as opposed to thawed ancient permafrost. Sources of dissolved methane under‐ice include a diffusive flux from the sediments and may include water column methanogenesis and/or under‐ice hydrodynamic controls. Following ice‐out, the water column only partially mixes allowing half of the winter‐derived dissolved methane to be microbially oxidized. Despite oxidation at depth, surface water was a source of methane to the atmosphere. The greatest diffusive fluxes to the atmosphere occurred following ice‐out (75 mmol CH4 m−2 d−1) and during a mixing episode in mid‐July, likely driven by a storm event. This study demonstrates the importance of fine‐scale temporal sampling to understand dissolved methane processes in seasonally ice‐covered lakes.

Carbon dioxide and methane exchange of a patterned subarctic fen during two contrasting growing seasons

Abstract. The patterned microtopography of subarctic mires generates a variety of environmental conditions, and carbon dioxide (CO2) and methane (CH4) dynamics vary spatially among different plant community types (PCTs). We studied the CO2 and CH4 exchange between a subarctic fen and the atmosphere at Kaamanen in northern Finland based on flux chamber and eddy covariance measurements in 2017–2018. We observed strong spatial variation in carbon dynamics between the four main PCTs studied, which were largely controlled by water table level and differences in vegetation composition. The ecosystem respiration (ER) and gross primary productivity (GPP) increased gradually from the wettest PCT to the drier ones, and both ER and GPP were larger for all PCTs during the warmer and drier growing season 2018. We estimated that in 2017 the growing season CO2 balances of the PCTs ranged from −20 g C m−2 (Trichophorum tussock PCT) to 64 g C m−2 (string margin PCT), while in 2018 all PCTs were small CO2 sources (10–22 g C m−2). We observed small growing season CH4 emissions (< 1 g C m−2) from the driest PCT, while the other three PCTs had significantly larger emissions (mean 7.9, range 5.6–10.1 g C m−2) during the two growing seasons. Compared to the annual CO2 balance (−8.5 ± 4.0 g C m−2) of the fen in 2017, in 2018 the annual balance (−5.6 ± 3.7 g C m−2) was affected by an earlier onset of photosynthesis in spring, which increased the CO2 sink, and a drought event during summer, which decreased the sink. The CH4 emissions were also affected by the drought. The annual CH4 balance of the fen was 7.3 ± 0.2 g C m−2 in 2017 and 6.2 ± 0.1 g C m−2 in 2018. Thus, the carbon balance of the fen was close to zero in both years. The PCTs that were adapted to drier conditions provided ecosystem-level resilience to carbon loss due to water level drawdown.

Infrared and Raman Spectroscopic Study of Methane Clathrate Hydrates at Low Temperatures and High Pressures: Dynamics and Cage Occupancy of Methane

Infrared (IR) absorption and Raman spectra of methane hydrate (MH) were measured at low temperatures and high pressures to reveal the dynamics and cage occupancy of CH4 molecules and the hydration numbers in phases I (MH-I), II (MH-II), and III (MH-III). For the IR spectra of MH-I below 40 K, bands assigned to the rovibrational transition appeared in the wavenumber region of the asymmetric stretching (ν3) mode of CH4 molecules in the M (51262) cages. This is evidence of the quasi-rotor behavior of CH4. The rovibrational bands were also observed in the IR spectra of MH-II below 1.3 GPa and below 40 K. Interestingly, the shapes of the totally symmetric stretching (ν1) and ν3 bands in the Raman and IR spectra of MH-II changed drastically above 1.3 GPa. This suggests that the cage occupancy of the LL (51268) cage changed from one to two via dehydration at 1.3 GPa. The hydration number also changed from 5.38 ± 0.05 to 4.80 ± 0.17 at 1.3 GPa. A doubly occupied state in the LL cage may arise from the formation of a dimer of CH4 molecules.

Dramatic temporal variations in methane levels in black bloom prone areas of a shallow eutrophic lake

Global lakes serve as a key natural source of methane (CH4) and suffer from increasing hypoxia due to unprecedented anthropogenic activities and climate change. A black bloom is a temporary hypoxia triggered by a longstanding algal bloom, which facilitates CH4 production by creating reducing conditions and abundant algae-sourced organic carbon. One-year investigations were conducted to examine temporal CH4 dynamics in the water and sediment pore water in black bloom prone areas (BBPAs) in Lake Taihu, China, where there had been at least two recorded black bloom events. The CH4 in the water changed significantly with time (p < 0.001), with the highest concentrations appearing in warm months when an abnormal lower dissolved oxygen content was observed at different sites, which were one to two orders of magnitude higher than other months. Compared with the control site, there were significantly higher CH4 concentrations in BBPA waters (p < 0.001), which was consistent with the higher CH4 in the sediment pore water. Methane dynamics in the water showed significant positive correlations with temperature, total phosphorus, total nitrogen, ammonia-N, and soluble reactive phosphorus (p < 0.05), but showed a significant inverse correlation with dissolved oxygen (p < 0.01). Redundancy analysis indicated dissolved oxygen made the largest contribution to CH4 dynamics in the BBPAs. A significant increase in the CH4 in water will turn BBPAs into temporary hot spots with substantial CH4 emissions with the appearance of black blooms. The results provide new insights into understanding future CH4 dynamics under globally prevailing algal blooms and climate change.

Dynamics of methane and other greenhouse gases flux in forest ecosystems in China

The article examines an important problem of studying greenhouse gas emissions in forest ecosystems. The CH4 emission and absorption dynamics in the soil have been studied based on the physical–chemical and microbiological analysis of forest products. The changes in forest methanogenesis in relation concerning the value of the hydrothermal coefficient have been examined. It was established that the most intensive emission of greenhouse gases was observed within the value of the hydrothermal coefficient (HTC) of 1.8 … 2. For soils with the HTC value of <1.3, almost no increase in greenhouse gases level was observed. It was found that fluctuations of methane levels in soil were seasonal. Statistical analysis of the obtained results showed sufficient convergence of the results. Thus, the determination coefficient of the obtained results was R 2 > 0.7, the Pearson criterion – χ 2 ∼ 1, and the Student’s t-criterion >0.8. The results showed that methane is almost completely absorbed by forest soils, while CO2 and N2O are released into the atmosphere. Laboratory studies of soil’s adsorption capacity relative to hydrocarbon under dynamic conditions have been performed and it has been established that soils with a high composition of organic matter showed significantly higher absorption capacity in comparison with sandy and clayey soils.

Broadband Time-Resolved Absorption and Dispersion Spectroscopy of Methane and Ethane in a Plasma Using a Mid-Infrared Dual-Comb Spectrometer.

Conventional mechanical Fourier Transform Spectrometers (FTS) can simultaneously measure absorption and dispersion spectra of gas-phase samples. However, they usually need very long measurement times to achieve time-resolved spectra with a good spectral and temporal resolution. Here, we present a mid-infrared dual-comb-based FTS in an asymmetric configuration, providing broadband absorption and dispersion spectra with a spectral resolution of 5 GHz (0.18 nm at a wavelength of 3333 nm), a temporal resolution of 20 μs, a total wavelength coverage over 300 cm−1 and a total measurement time of ~70 s. We used the dual-comb spectrometer to monitor the reaction dynamics of methane and ethane in an electrical plasma discharge. We observed ethane/methane formation as a recombination reaction of hydrocarbon radicals in the discharge in various static and dynamic conditions. The results demonstrate a new analytical approach for measuring fast molecular absorption and dispersion changes and monitoring the fast dynamics of chemical reactions over a broad wavelength range, which can be interesting for chemical kinetic research, particularly for the combustion and plasma analysis community.

Shifts in methanogenic archaea communities and methane dynamics along a subtropical estuarine land use gradient.

In coastal aquatic ecosystems, prokaryotic communities play an important role in regulating the cycling of nutrients and greenhouse gases. In the coastal zone, estuaries are complex and delicately balanced systems containing a multitude of specific ecological niches for resident microbes. Anthropogenic influences (i.e. urban, industrial and agricultural land uses) along the estuarine continuum can invoke physical and biochemical changes that impact these niches. In this study, we investigate the relative abundance of methanogenic archaea and other prokaryotic communities, distributed along a land use gradient in the subtropical Burnett River Estuary, situated within the Great Barrier Reef catchment, Australia. Microbiological assemblages were compared to physicochemical, nutrient and greenhouse gas distributions in both pore and surface water. Pore water samples from within the most urbanised site showed a high relative abundance of methanogenic Euryarchaeota (7.8% of all detected prokaryotes), which coincided with elevated methane concentrations in the water column, ranging from 0.51 to 0.68 μM at the urban and sewage treatment plant (STP) sites, respectively. These sites also featured elevated dissolved organic carbon (DOC) concentrations (0.66 to 1.16 mM), potentially fuelling methanogenesis. At the upstream freshwater site, both methane and DOC concentrations were considerably higher (2.68 μM and 1.8 mM respectively) than at the estuarine sites (0.02 to 0.66 μM and 0.39 to 1.16 mM respectively) and corresponded to the highest relative abundance of methanotrophic bacteria. The proportion of sulfate reducing bacteria in the prokaryotic community was elevated within the urban and STP sites (relative abundances of 8.0%- 10.5%), consistent with electron acceptors with higher redox potentials (e.g. O2, NO3-) being scarce. Overall, this study showed that ecological niches in anthropogenically altered environments appear to give an advantage to specialized prokaryotes invoking a potential change in the thermodynamic landscape of the ecosystem and in turn facilitating the generation of methane-a potent greenhouse gas.

Nitrous oxide and methane emissions from beef cattle excreta deposited on feedlot pen surface in tropical conditions

As feedlot beef production systems are expanding into tropical climates, considerably less is known on their environmental impact specific to these regions. Our objective was to investigate the dynamics of nitrous oxide (N2O) and methane (CH4) fluxes in a feedlot system representative of Brazil, in order to aggregate new emission data for the characterization of intensive cattle raising in tropical regions. Excreta was obtained from Nellore steers in a feedlot (n = 25, BW = 393 ± 31 kg). Urine (1.3 L) and feces (1.3 kg) were applied separately in plots on an open-lot feedlot pen surface at the beginning of the trial and fluxes were monitored 92 d with static chambers. Although CH4 fluxes were variable, all treatments were a sink for CH4 as the average of the monitoring period (−8.9, −3.1, and −15.4 μg C m−2 h−1 for feces, urine, and control, respectively). The N2O fluxes were higher in the urine affected area, which was related to the higher soil moisture and mineral N availability in comparison to the area with feces. The occurrence of rainfall from 67 to 70 DAA was determinant of very high N2O fluxes either for urine or feces. Hence, GHG emissions from individual excreta were characterized by a period of small but significant fluxes, followed by a period of indistinguishable fluxes at the background level. A third period after rainfall portrayed the large impact of excreta on GHG emissions from the feedlot. The direct N2O emission factor (EF) for the N in urine was significantly higher than for the N in feces (2.83 vs. 0.32%, respectively, P < 0.0001), and combining both resulted in an EF for the N in excreta of 1.83%, which is 8.5% less than IPCC default EF for dry lot systems. From the calculated direct emissions of N2O, gas monitoring of urine and feces in separate should be also considered for the development of emission factors for inventory purposes in tropical environments. For the regions where feedlots are used in the dry season for finishing cattle, cleaning pens regularly can contribute substantially to mitigate N2O emissions as suggested by the results of the present study.

Reorientational dynamics of molecules in liquid methane: A molecular dynamics simulation study

Rotational motion of molecules in liquids plays an important role in determining the liquids' Nuclear Magnetic Resonance (NMR) spin-relaxation properties. The traditional theory of NMR spin relaxation assumes that the reorientational dynamics of molecules in liquids can be described by a continuous-time rotational-diffusion random walk with a single rotational-diffusion coefficient. However, recent experimental and theoretical studies have demonstrated that the simple rotational-diffusion model does not fully capture the rotational dynamics of molecules in liquids: for example, the reorientation of molecules in liquid water occurs through a combination of continuous-time rotational diffusion and discrete, large angular jumps resulting from collective rearrangements of the hydrogen-bond network of water.In order to obtain further insights into the origin of large angular jumps in the rotational motion of liquid water, we studied the rotational dynamics of methane - an apolar, non‑hydrogen-bonding liquid with a spherically symmetric molecule. The reorientational propagator and the ensemble-averaged Legendre polynomial reorientational functions of liquid methane were analysed using molecular dynamics simulations. On the femtosecond timescale, the reorientational motion of methane molecules was found to be characterised by free-rotation gas-like Gaussian decay of the reorientational Legendre polynomials, a result consistent with the available experimental data for liquid methane. On the long timescale (picoseconds) the decay of the reorientational Legendre polynomials was exponential, suggestive of a Debye-like continuous-time rotational diffusion behaviour. However, the ratios of the exponential time constants for different orders of the Legendre polynomials failed to match the rotational-diffusion model. We discuss the implications of these findings for the understanding of rotational motion of molecules in hydrogen-bonding and non‑hydrogen-bonding liquids.

Seasonal patterns of greenhouse gas emissions from a forest‐to‐bog restored site in northern Scotland: Influence of microtopography and vegetation on carbon dioxide and methane dynamics

AbstractNorthern peatlands play an important role in the regulation of the atmospheric greenhouse gas (GHG) balance, functioning as a net carbon sink with low rates of organic decomposition. However, perturbations such as drainage increase peat oxidation, which may lead to enhanced gaseous release of carbon. For this reason, the number of restoration projects that aim to rewet blanket bogs has increased in the last few years, but there is still a lack of understanding of the impact of restoration on emissions of greenhouse gases, such as methane, particularly in sites restored from forestry. In this paper, we investigate the seasonal greenhouse gas dynamics in a forest‐to‐bog restoration site in Scotland. We analyse the effects of restoration on both carbon dioxide and methane fluxes, and investigate which site factors (microtopography, vegetation type, soil moisture and temperature) drive the processes of gaseous exchange between the bog surface and the atmosphere. Our results show that the original surface is near greenhouse gase equilibrium at −0.28 gCO2eq m2·day−1 and that microtopographic features act as a net greenhouse gas sink (ridges = −0.94 gCO2eq m2·day−1 and furrows = −0.86 gCO2eq m2·day−1), whereas the bog pool is a net source of greenhouse gases (0.98 gCO2eq m2·day−1). We found different vegetation species play a key role in greenhouse gas flux dynamics, especially in forestry‐derived microtopographical features, and their presence and influence on greenhouse gas dynamics should be accounted for to provide a more comprehensive understanding of emissions associated with restoration management practices.Highlights GHG (CO2 and CH4) dynamics in a boreal peatland restored from forestry are mainly affected by microtopography and vegetation. Forestry‐derived microforms (ridges and furrows) are better GHG sinks than pools (GHG emitters) and original surfaces (near GHG equilibrium). The presence of Trichophorum cespitosum leads to higher CH4 emissions. Restoration practices like terraforming may create a short‐term pulse net GHG emission due to an increase of both CH4 and CO2 fluxes.

Multi-proxy approach to unravel methane emission history of an Arctic cold seep

Arctic Ocean sediments contain large amounts of methane in the form of free gas and gas hydrate. This highly dynamic methane reservoir is susceptible to be modified by bottom water warming. The warming may lead to gas hydrate destabilization releasing elevated methane fluxes to the seafloor and seawater. Reconstructing past methane dynamics can be achieved by using specific proxies left in the geological record. In this study, we apply a multi-proxy approach for paleo seepage reconstruction from sediment records at gas hydrate mounds (GHMs) in Storfjordrenna (south of the Svalbard archipelago). These shallow water (∼380 m water depth) systems are potentially vulnerable to global warming related temperature changes. 14C dating of foraminifera shells indicated an onset of deglaciation in the Storfjordrenna region at ∼20 kyr BP and allowed us to establish a stratigraphic context based on sediment Zr/Rb and Fe/Ca ratios. Several major (between 15 and 17 kyr BP) and minor methane venting phases were identified and interpreted to be related to gas hydrate instability triggered by isostatic adjustment right after the onset of the deglaciation. The detection of all major methane releases was only possible by combining data sets of stable carbon isotope compositions of foraminifera, mineralogy and δ13C values of authigenic carbonates, and abundance and stable carbon isotope signatures of lipid biomarkers. The most robust single proxy in this study was provided by the δ13C values of archaeal biomarkers. In contrast, the sediment Ba/Ti ratios recorded only the major events. Our results highlight the complexity and heterogeneity of methane dynamics in a small area of some hundred meters across.

Methane Seeps and Independent Methane Plumes in the South China Sea Offshore Taiwan

In the northern South China Sea (SCS) we explored methane dynamics in the water column during SONNE-cruise SO266 in October/November 2018. Two depth zones contained elevated methane concentrations: the upper 400 m ( 10°C and > 20°C, respectively. Both 16S rRNA gene and pmoA amplicon analyses revealed distinct microbial and methanotrophic communities in water with temperature of 27°C, ~10°C, and 3°C. Second, we found elevated methane concentrations in 200-400 m in the FWCR-region whereas increased methane concentrations occurred in the uppermost 100 m above SSFR. The deeper plume above FWCR might be due to an intrusion of the Kuroshio water mass into SCS keeping the methane from being aerobically oxidized in the warm surface water and vented to the atmosphere. Finally, all peak methane concentrations occurred in water depth, with rather low backscatter, i.e. in water depth with less suspended matter. At the seafloor, ocean currents and long-term seepage appeared to control methane dynamics. We derived methane fluxes of 0.08-0.12 mmol m-2 d-1 from a 4.5 km2 area at FWCR and of 3.0-79.9 mmol m-2 d-1 from a 0.01 km2 area at SSFR. Repetitive sampling of the area at SSFR indicated that changing directions of ocean currents possibly affected methane concentrations and thus flux. In contrast to these seepage sites with distinct methane plumes, retrieval of drilling equipment produced no methane plume. Even gas emission triggered by seafloor drilling did not supply measureable methane concentrations after 3 hours, but caused an increase in methanotrophic activity as determined by rate measurements and molecular-biological analyses. Apparently, only long-term seepage can generate methane anomalies in the ocean.

Methane oxidation potential of the arctic wetland soils of a taiga-tundra ecotone in northeastern Siberia

ABSTRACT Arctic wetlands are significant sources of atmospheric methane and the observed accelerated climate changes in the arctic could cause a change in methane dynamics. Methane oxidation would be the key process to control methane emission from wetlands. In this study, we determined the potential methane oxidation rate of the wetland soils of a taiga–tundra transition zone in northeastern Siberia. Peat soil samples were collected in summer from depressions covered with tussocks of sedges and Sphagnum spp. and from mounds vegetated with moss and larch trees. An aerobic bottle incubation experiment demonstrated that the soil samples collected from depressions in the moss- and sedge-dominated zones exhibited active methane oxidation with no time lag, while the mound soils showed no methane oxidation under the given conditions. The potential methane oxidation rates of the soils at 15°C ranged from 94 to 496 nmol h−1 g−1 dw. The immediate and active methane oxidation was observed over the depths studied (0–40 cm) including the water-saturated anoxic layers; the maximum methane oxidation rate was recorded in the layer above the water-saturated layer. The methane oxidation rate was temperature-dependent, but substantial methane oxidation was observed even at 0°C particularly for the moss soil samples. Soil samples collected from the frozen layer of Sphagnum peat also showed immediate methane consumption when incubated at 15°C. The present results suggest that the methane oxidizing bacteria in the wetland soils could survive under anoxic and frozen conditions keeping their potential activities and immediately utilize methane when the conditions become favorable. On the other hand, the inhibitor of methane oxidation (difluoromethane) did not affect the methane flux from the sedge and moss zones in situ, which suggested the minor role of plant-associated methane oxidation.

Spectral evidence for substrate availability rather than environmental control of methane emissions from a coastal forested wetland

Knowledge of the dynamics of methane (CH4) fluxes across coastal freshwater forested wetlands, such as those found in the southeastern US remains limited. In the current study, we look at the spectral properties of ecosystem net CH4 exchange (NEECH4) time series, and its cospectral behavior with key environmental conditions (temperature (Ts5), water table (WTD) and atmospheric pressure (Pa)) and physiological fluxes (photosynthesis (GPP), transpiration (LE), sap flux (Js)) using data from a natural bottomland hardwood swamp in eastern North Carolina. NEECH4 fluxes were measured over five years (2012 – 2016) that included both wet and dry years. During the growing season, strong cospectral peaks at diurnal scale were detected between CH4 efflux and GPP, LE and Js. This suggests that the well understood diurnal cycles in the latter processes may affect CH4 production through substrate availability (GPP) and transport (sap flow and LE). The causality between different time series was established by the magnitude and consistency of phase shifts. The causal effect of Ts5 and Pa were ruled out because despite cospectral peaks with CH4, their phase relationships were inconsistent. The effect of fluctuations in WTD on CH4 efflux at synoptic scale lacked clear indications of causality, possibly due to time lags and hysteresis. The stronger cospectral peak with ecosystem scale LE rather than Js suggested that the evaporative component of LE contributed equally with plant transpiration. Hence, we conclude that while the emission of dissolved gases through plants likely takes place, it may not contribute to higher CH4 emissions as has been proposed by aerenchymatous gas transport in sedge wetlands. These findings can inform future model development by (i) highlighting the coupling between vegetation processes and CH4 emissions, and (ii) identifying specific and non-overlapping timescales for different driving factors.

Influence of ventilation in H2S exposure and emissions from a gravity sewer.

This study was carried out to evaluate the effect of natural ventilation and intermittent pumping events in hydrogen sulfide and methane dynamics, in terms of system operation and risk of gas exposure. Work was conducted in a full scale gravity sewer downstream of pumping stations, in Portugal. Different ventilation rates and locations were assessed, as well as H2S removal rates and potential exposure risk, through the opening of distinct manhole covers. Increased ventilation, resulting from opening of one manhole cover, saw a 38% increase in average pipe air velocity peaks, doubling the estimated rate of air turnovers per day, accompanied by an increase of nearly 20% in H2S average removal rate. Simultaneous opening of two manhole covers induced similar airflow rates through the vent stack, but different rates throughout the pipe. H2S removal rates were also found to differ, according to location of open manholes, but also initial H2S headspace concentration. Under more unfavourable conditions, natural ventilation did not suffice in attaining recommended safety concentrations, regardless of number and location of open manhole covers. H2S concentrations above defined thresholds were verified for all studied setups. Headspace oxygen concentrations below an 18.5% asphyxiation threshold also occasionally occurred, even at manholes immediately downstream of ventilation point.

Methane oxidation dynamics in a karst subterranean estuary

Chemical gradients between fresh, brackish and saline waters shape biogeochemical reactions and organic matter transformation within subterranean estuaries. In the Yucatán Peninsula’s karst subterranean estuary (KSE), methane and dissolved organic matter generated during the anaerobic decomposition of tropical forest vegetation are transported into flooded cave networks where microbial consumption greatly reduces their concentrations in the groundwater. To test the hypothesis that chemoclines associated with salinity gradients of the KSE are sites of methane oxidation, we obtained methane concentration and δ13C profiles of unprecedented vertical resolution from within a fully-submerged cave system located 6.6 km inland from the coastline using the ‘OctoPiPi’ (OPP) water sampler. Along a 12–24 cm thick low-salinity-halocline at ∼4.5 m water depth, salinity increased from fresh to brackish (0.2–1.8 psu), methane concentrations decreased, and δ13C values increased, as expected for microbial methane oxidation. The underlying brackish water had elevated oxygen concentrations compared to the always anoxic freshwater, suggesting that aerobic methane oxidation is the dominant process facilitating methane consumption. By contrast, as salinity increased from 1.8 to 36 psu through a 24–36 cm thick high-salinity-halocline between the meteoric lens and the saline groundwater at ∼20 m water depth, methane concentrations and δ13C values were constant. Conservative mixing and kinetic isotope models incorporating the methane data confirm a hotspot for microbial methane oxidation at the low-salinity-halocline. At least 98% of methane originating in the anoxic freshwaters was removed before its transport via channelized flow towards the coastline. These findings provide novel insight into the spatial constraints of methane dynamics within a karst subterranean estuary.

A Quantitative Assessment of Methane-Derived Carbon Cycling at the Cold Seeps in the Northwestern South China Sea

Widespread cold seeps along continental margins are significant sources of dissolved carbon to the ocean water. However, little is known about the methane turnovers and possible impact of seepage on the bottom seawater at the cold seeps in the South China Sea (SCS). We present seafloor observation and porewater data of six push cores, one piston core and three boreholes as well as fifteen bottom-water samples collected from four cold seep areas in the northwestern SCS. The depths of the sulfate–methane transition zone (SMTZ) are generally shallow, ranging from ~7 to &lt;0.5 mbsf (meters below seafloor). Reaction-transport modelling results show that methane dynamics were highly variable due to the transport and dissolution of ascending gas. Dissolved methane is predominantly consumed by anaerobic oxidation of methane (AOM) at the SMTZ and trapped by gas hydrate formation below it, with depth-integrated AOM rates ranging from 59.0 and 591 mmol m−2 yr−1. The δ13C and Δ14C values of bottom-water dissolved inorganic carbon (DIC) suggest discharge of 13C- and 14C-depleted fossil carbon to the bottom water at the cold seep areas. Based on a two-endmember estimate, cold seeps fluids likely contribute 16–26% of the bottom seawater DIC and may have an impact on the long-term deep-sea carbon cycle. Our results reveal the methane-related carbon inventories are highly heterogeneous in the cold seep systems, which are probably dependent on the distances of the sampling sites to the seepage center. To our knowledge, this is the first quantitative study on the contribution of cold seep fluids to the bottom-water carbon reservoir of the SCS, and might help to understand the dynamics and the environmental impact of hydrocarbon seep in the SCS.

Methane emissions from fens in Alberta’s boreal region: reference data for functional evaluation of restoration outcomes

The aim of the study was to document methane (CH4) dynamics from fen ecosystems in the Athabasca Oil Sands Region (AOSR) in northern Alberta to create a reference database for evaluation of peatland restoration and reclamation projects in the region. The study included three types of fens commonly occurring in this region: poor fen (open and treed), moderately-rich treed fen, and open saline fen (SF). We quantified CH4 fluxes, pore water concentration (PW[CH4]), and production potential together with ecohydrological variables that may influence CH4 dynamics over four growing seasons. Mean (standard deviation) fluxes for open and treed poor fen [99.8 (269.7) and 68.3 (118.8) mg CH4 m−2 day−1, respectively] were higher than for treed rich [32.8 (63.7) mg CH4 m−2 day−1] and open SFs [34.6 (91.3) mg CH4 m−2 day−1]. The total growing season CH4 emissions from these fens ranged between 3.7 and 11.3 g CH4 m−2. Methane production potential varied from 0.1 (0.1) µmol CH4 g peat−1 day−1 at the SF to 4.6 (0.8) µmol CH4 g peat−1 day−1 at the treed rich fen. The variability of CH4 fluxes and pore water concentration between study sites and years was mostly controlled water table (WT) and soil temperature indicating that these variables should be used to assess the expected CH4 flux in peatland reclamation projects. Large inter-annual variability in CH4 flux illustrates the importance of multi-year records for data used in functional evaluation of restoration outcomes.

Methane dynamics in the coastal – Continental shelf transition zone of the Gulf of Cadiz

The concentration of CH4 in water was measured along five transects in the Gulf of Cadiz (Trafalgar, Sancti Petri, Guadalquivir, Tinto - Odiel and Guadiana) during four cruises throughout the months of March, June, September and December 2016. For two of the cruises water overlying three mud volcanoes situated in the Gulf of Cadiz were also sampled (San Petersburgo, 860 m; Pipoca, 460 m; and Anastasya, 500 m. In addition, the stable carbon isotopic compositions of dissolved CH4 (δ13C) were measured in the study area in June and December 2016. The mean CH4 value for the whole water column was 10.5 ± 4.3 nmol L−1, with large spatial and temporal variations. The highest values were found in June 2016 and the lowest in March 2016. In surface waters, the mean dissolved methane concentration was of 9.6 ± 2.6 nmol L−1. In most of the sampling area, high concentrations of CH4 were found in subsurface waters at depths close to the thermocline and at the coastal stations. The highest concentrations were obtained from the bottom waters above the Anastasya mud volcano (125 nmol L−1). The stable carbon isotope compositions ranged between - 29.2 and - 58.4‰, and the least negative values were associated with the highest CH4 concentrations in samples from above the mud volcanoes, related to thermogenic values. The sea-air fluxes of CH4 ranged from 12.4 to 37.7 μmol m−2 d−1, showing that the study area acts as a source of CH4 to the atmosphere.