Soil methane sink capacity response to a long-term wildfire chronosequence in Northern Sweden

Boreal forests occupy nearly one fifth of the terrestrial land surface and are recognised as globally important regulators of carbon (C) cycling and greenhouse gas emissions. Carbon sequestration processes in these forests include assimilation of CO2 into biomass and subsequently into soil organic matter, and soil microbial oxidation of methane (CH4). In this study we explored how ecosystem retrogression, which drives vegetation change, regulates the important process of soil CH4 oxidation in boreal forests. We measured soil CH4 oxidation processes on a group of 30 forested islands in northern Sweden differing greatly in fire history, and collectively representing a retrogressive chronosequence, spanning 5000 years. Across these islands the build-up of soil organic matter was observed to increase with time since fire disturbance, with a significant correlation between greater humus depth and increased net soil CH4 oxidation rates. We suggest that this increase in net CH4 oxidation rates, in the absence of disturbance, results as deeper humus stores accumulate and provide niches for methanotrophs to thrive. By using this gradient we have discovered important regulatory controls on the stability of soil CH4 oxidation processes that could not have not been explored through shorter-term experiments. Our findings indicate that in the absence of human interventions such as fire suppression, and with increased wildfire frequency, the globally important boreal CH4 sink could be diminished

Activity of type I methanotrophs dominates under high methane concentration: methanotrophic activity in slurry surface crusts as influenced by methane, oxygen, and inorganic nitrogen

Livestock slurry is a major source of atmospheric methane (CH4), but surface crusts harboring methane-oxidizing bacteria (MOB) could mediate against CH4 emissions. This study examined conditions for CH4 oxidation by in situ measurements of oxygen (O2) and nitrous oxide (N2O), as a proxy for inorganic N transformations, in intact crusts using microsensors. This was combined with laboratory incubations of crust material to investigate the effects of O2, CH4, and inorganic N on CH4 oxidation, using 13CH4 to trace C incorporation into lipids of MOB. Oxygen penetration into the crust was 2 to 14 mm, confining the potential for aerobic CH4 oxidation to a shallow layer. Nitrous oxide accumulated within or below the zone of O2 depletion. With 102 ppmv CH4 there was no O2 limitation on CH4 oxidation at O2 concentrations as low as 2%, whereas CH4 oxidation at 104 ppmv CH4 was reduced at ≤5% O2. As hypothesized, CH4 oxidation was in general inhibited by inorganic N, especially NO2–, and there was an interaction between N inhibition and O2 limitation at 102 ppmv CH4, as indicated by consistently stronger inhibition of CH4 oxidation by NH4+ and NO3– at 3% compared with 20% O2. Recovery of 13C in phospholipid fatty acids suggested that both Type I and Type II MOB were active, with Type I dominating high-concentration CH4 oxidation. Given the structural heterogeneity of crusts, CH4 oxidation activity likely varies spatially as constrained by the combined effects of CH4, O2, and inorganic N availability in microsites

Methane concentration and isotopic composition (d13C-CH4) in the Nerja Cave system (South Spain)

Air in underground caves often has methane (CH4) concentrations below the atmospheric level, due to methanotrophic or other unkown CH4 consuming processes. Caves are thus considered a potential sink for atmospheric methane. If globally important, this underground CH4 oxidation should be taken into account in the atmospheric methane budget, in addition to the known soil methanotrophy and tropospheric/stratospheric sinks. A large set of data is however necessary to understand how and how much methane from external atmospheric air is consumed in the caves. While methane concentration data are available for several caves worldwide, its isotopic composition and variations in space and time are poorly documented. We measured methane concentration and stable C isotope composition (d13C) in the Nerja cave (Southern Spain) air during two surveys in March and April 2015. CH4 concentration decreases progressively from the more external cave rooms, with atmospheric levels of 1.9 ppmv, to the more internal and isolated rooms down to 0.5 ppmv. d13C increases correspondingly from -47 h to -41 h (VPDB). CH4 is systematically 13C-enriched (d13C > -45 permil) in areas of the cave where the concentration is below 1.4 ppmv. This combination of concentration decrease and 13C-enrichment towards the more internal and isolated zones of the cave confirms the importance of CH4 oxidation, likely driven by methanotrophic bacteria. Further data, including stable H isotope composition of subatmospheric CH4 concentrations, CO2 and microbial analyses, shall be acquired over time to assess the actual role of methanotrophic bacteria and seasonal controls in the CH4 consumption process.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Quantification of methane oxidation in the rice rhizosphere using 13C-labelled methane

In this paper isotope ratio mass spectrometry is used to determine the methane (CH4) oxidation fraction in the rhizosphere of intact rice plant-soil systems. Earlier studies on quantification of the methane oxidation were based on inhibition or incubation procedures which strongly interfered with the plant-soil system and resulted in a large variability of the reported fractions, while other studies considered stable isotopes at natural abundance levels to investigate methanotrophy in the rhizosphere of rice. The current work is the first that used 13C-labelled CH4 as additive and calculated the oxidation fraction from the ratio between the added 13C-labelled CH4 and its oxidation product 13CO2. Both labelled gases could be distinguished from the natural abundance percentages. The oxidation fraction for methane was found to be smaller than 7%, suggesting that former approaches overestimate the methane oxidation fraction.

Effect of Carex rostrata on seasonal and interannual variability in peatland methane emissions

Peatlands are a large natural source of atmospheric methane (CH4), and the sedge Carex rostrata plays a critical role in the production, oxidation, and transport of CH4 in these systems. This 4 year clipping experiment examined the changes in CH4 emissions from a temperate peatland after removing all aboveground C. rostrata biomass. Methane fluxes, dissolved CH4, and environmental variables were measured during spring, summer, and fall from 2008 to 2011. Clipping and removing the C. rostrata leaves and stems caused an immediate decrease in CH4 emissions that persisted over 4 years of this study. There was a strong seasonal trend in CH4 flux, with the largest treatment effects occurring during the fall months when the sedges were senescing. As expected, there was a strong positive correlation between C. rostrata green-leaf area and CH4 flux, implying that the presence of C. rostrata increases CH4 emissions from this peatland. Large interannual variability in vegetation distribution and biomass, water table depth, and temperature was observed in this study, indicating the importance of multiyear studies for understanding the interactions among these factors to determine how they could be incorporated into biogeochemical models to predict CH4 emissions under changing environmental conditions

Simulation of hydrogen production for mobile fuel cell applications via autothermal reforming of methane

This paper presents a simulation of catalytic autothermal reforming (ATR) of methane (CH4) for hydrogen (H2) production. ATR is essentially an oxidative steam reforming, which combines the exothermic partial oxidation (PO) with the endothermic steam reforming (SR) under thermally neutral conditions. A model is developed using HYSYS 2004.1 to simulate the conversion behavior of the reformer. The model covers all aspects of major chemical kinetics and heat and mass transfer phenomena in the reformer. The ATR and preferential oxidation (PrOx) processes is modeled using conversion reactor, while the water gas shift (WGS) process is modeled using equilibrium reactor within HYSYS environment. The conditions used for high CH4 conversion and high H2 yield are at air to fuel ratio of 2.5 and water to fuel ratio of 1.5. Under this condition, CH4 conversion of 100% and H2 yield of 44% on wet basis can be achieved and the system efficiency is about 87.7%

Heavy hydrogen in the stratosphere

We report measurements of the deuterium content of molecular hydrogen (H2) obtained from a suite of air samples that were collected during a stratospheric balloon flight between 12 and 33 km at 40º N in October 2002. Strong deuterium enrichments of up to 400 permil versus Vienna Standard Mean Ocean Water (VSMOW) are observed, while the H2 mixing ratio remains virtually constant. Thus, as hydrogen is processed through the H2 reservoir in the stratosphere, deuterium is accumulated in H2 . Using box model calculations we investigated the effects of H2 sources and sinks on the stratospheric enrichments. Results show that considerable isotope enrichments in the production of H2 from CH4 must take place, i.e., deuterium is transferred preferentially to H2 during the CH4 oxidation sequence. This supports recent conclusions from tropospheric H2 isotope measurements which show that H2 produced photochemically from CH4 and non-methane hydrocarbons must be enriched in deuterium to balance the tropospheric hydrogen isotope budget. In the absence of further data on isotope fractionations in the individual reaction steps of the CH4 oxidation sequence, this effect cannot be investigated further at present. Our measurements imply that molecular hydrogen has to be taken into account when the hydrogen isotope budget in the stratosphere is investigated

Biotechnological aspects of sulfate reduction with methane as electron donor

Biological sulfate reduction can be used for the removal and recovery of oxidized sulfur compounds and metals from waste streams. However, the costs of conventional electron donors, like hydrogen and ethanol, limit the application possibilities. Methane from natural gas or biogas would be a more attractive electron donor. Sulfate reduction with methane as electron donor prevails in marine sediments. Recently, several authors succeeded in cultivating the responsible microorganisms in vitro. In addition, the process has been studied in bioreactors. These studies have opened up the possibility to use methane as electron donor for sulfate reduction in wastewater and gas treatment. However, the obtained growth rates of the responsible microorganisms are extremely low, which would be a major limitation for applications. Therefore, further research should focus on novel cultivation technique

Assessing connectivity between an overlying aquifer and a coal seam gas resource using methane isotopes, dissolved organic carbon and tritium

Coal seam gas (CSG) production can have an impact on groundwater quality and quantity in adjacent or overlying aquifers. To assess this impact we need to determine the background groundwater chemistry and to map geological pathways of hydraulic connectivity between aquifers. In south-east Queensland (Qld), Australia, a globally important CSG exploration and production province, we mapped hydraulic connectivity between the Walloon Coal Measures (WCM, the target formation for gas production) and the overlying Condamine River Alluvial Aquifer (CRAA), using groundwater methane (CH4) concentration and isotopic composition (δ13C-CH4), groundwater tritium (3H) and dissolved organic carbon (DOC) concentration. A continuous mobile CH4 survey adjacent to CSG developments was used to determine the source signature of CH4 derived from the WCM. Trends in groundwater δ13C-CH4 versus CH4 concentration, in association with DOC concentration and 3H analysis, identify locations where CH4 in the groundwater of the CRAA most likely originates from the WCM. The methodology is widely applicable in unconventional gas development regions worldwide for providing an early indicator of geological pathways of hydraulic connectivity