Unraveling the catalytic performance of RuO2(1 1 0) for highly-selective ethylene production from methane at low temperature: Insights from first-principles and microkinetic simulations.

Despite significant progress in low-temperature methane (CH4) activation, commercial viability, specifically obtaining high yields of C1/C2 products, remains a challenge. High desorption energy (>2 eV) and overoxidation of the target products are key limitations in CH4 utilization. Herein, we employ first-principles density functional theory (DFT) and microkinetics simulations to investigate the CH4 activation and the feasibility of its conversion to ethylene (C2H4) on the RuO2 (1 1 0) surface. The CH activation and CH4 dehydrogenation processes are thoroughly investigated, with a particular focus on the diffusion of surface intermediates. The results show that the RuO2 (1 1 0) surface exhibits high reactivity in CH4 activation (Ea = 0.60 eV), with CH3 and CH2 are the predominant species, and CH2 being the most mobile intermediate on the surface. Consequently, self-coupling of CH2* species via CC coupling occurs more readily, yielding C2H4, a potential raw material for the chemical industry. More importantly, we demonstrate that the produced C2H4 can easily desorb under mild conditions due to its low desorption energy of 0.97 eV. Microkinetic simulations based on the DFT energetics indicate that CH4 activation can occur at temperatures below 200 K, and C2H4 can be desorbed at room temperature. Further, the selectivity analysis predicts that C2H4 is the major product at low temperatures (300-450 K) with 100 % selectivity, then competes with formaldehyde at intermediate temperatures in the CH4 conversion over RuO2 (1 1 0) surface. The present findings suggest that the RuO2 (1 1 0) surface is a potential catalyst for facilitating ethylene production under mild conditions.

Increasing electrochemical carbon dioxide reduction to methane via a novel copper-based conductive metal organic framework.

The development of a new system for the electrochemical carbon dioxide reduction reaction (ECO2RR) to methane (CH4) is challenging, and novel conductive metal organic frameworks (c-MOFs) for efficient ECO2RR to CH4 are critical to this system. Here, we report a novel c-MOF, copper-pyromellitic dianhydride-2-methylbenzimidazole (Cu-PD-2-MBI), in which the introduction of electron-withdrawing 2-methylbenzimidazole (2-MBI) into the copper-pyromellitic dianhydride (Cu-PD) interlayer elevated the valence of copper (Cu) ions, which improved the ECO2RR performance of Cu-PD-2-MBI. Cu-PD-2-MBI was tested in a flow cell, and the Faradaic efficiency of CH4 reached 73.7 %, with a corresponding partial current density of -428.3 mA·cm-2 at -1.3 V, which was higher than those of most reported Cu-based catalysts. Further exploration via theoretical calculations indicated that the intercalated 2-MBI in Cu-PD-2-MBI induced a shift in the d-band center in the Cu sites from -2.63 to -1.86 eV and reduced the formation energy of the *COOH and *CHO intermediates in the process of generating CH4 compared with those of the reference Cu-PD catalyst.

Iron-promoted zirconia-alumina supported Ni catalyst for highly efficient and cost-effective hydrogen production via dry reforming of methane.

Developing cost-effective and high-performance catalyst systems for dry reforming of methane (DRM) is crucial for producing hydrogen (H2) sustainably. Herein, we investigate using iron (Fe) as a promoter and major alumina support in Ni-based catalysts to improve their DRM performance. The addition of iron as a promotor was found to add reducible iron species along with reducible NiO species, enhance the basicity and induce the deposition of oxidizable carbon. By incorporating 1 wt.% Fe into a 5Ni/10ZrAl catalyst, a higher CO2 interaction and formation of reducible "NiO-species having strong interaction with support" was observed, which led to an ∼80% H2 yield in 420 min of Time on Stream (TOS). Further increasing the Fe content to 2wt% led to the formation of additional reducible iron oxide species and a noticeable rise in H2 yield up to 84%. Despite the severe weight loss on Fe-promoted catalysts, high H2 yield was maintained due to the proper balance between the rate of CH4 decomposition and the rate of carbon deposit diffusion. Finally, incorporating 3 wt.% Fe into the 5Ni/10ZrAl catalyst resulted in the highest CO2 interaction, wide presence of reducible NiO-species, minimum graphitic deposit and an 87% H2 yield. Our findings suggest that iron-promoted zirconia-alumina-supported Ni catalysts can be a cheap and excellent catalytic system for H2 production via DRM.

In situ DRIFTs-based comprehensive reaction mechanism of photo-thermal synergetic catalysis for dry reforming of methane over Ru-CeO2 catalyst.

Solar-driven photo-thermal dry reforming of methane (DRM) is an environmentally friendly production route for high-value-added chemicals. However, the lack of thorough understanding of the mechanism for photo-thermal reaction has limited its further development. Here, we systematically investigated the mechanism of photo-thermal DRM reaction with the representative of Ru/CeO2 catalyst. Through in situ DRIFTs and transient experiments, comprehensive investigation into the reaction steps and their reactive sites in the process of DRM reaction were conducted. Besides, the excitation and migration direction of photo-electron was determined by ISI-XPS experiments, and the change of surface defect structure induced by light was characterized by ISI-EPR experiments. Based on the above results, the photo-enhancement effect on each micro-reaction step was determined. This study provides a theoretical basis for the industrialization of photo-thermal DRM reaction and its development of catalysts.

Hydrogen production from dry reforming of methane, using CO2 previously chemisorbed in the Li6Zn1-xNixO4 solid solution.

Li6ZnO4 was chemically modified by nickel addition, in order to develop different compositions of the solid solution Li6Zn1-xNixO4. These materials were evaluated bifunctionally; analyzing their CO2 capture performances, as well as on their catalytic properties for H2 production via dry reforming of methane (DRM). The crystal structures of Li6Zn1-xNixO4 solid solution samples were determined through X-ray diffraction, which confirmed the integration of nickel ions up to a concentration around 20 mol%, meanwhile beyond this value, a secondary phase was detected. These results were supported by XPS and TEM analyses. Then, dynamic and isothermal thermogravimetric analyses of CO2 capture revealed that Li6Zn1-xNixO4 solid solution samples exhibited good CO2 chemisorption efficiencies, similarly to the pristine Li6ZnO4 chemisorption trends observed. Moreover, a kinetic analysis of CO2 isothermal chemisorptions, using the Avrami-Erofeev model, evidenced an increment of the constant rates as a function of the Ni content. Since Ni2+ ions incorporation did not reduce the CO2 capture efficiency and kinetics, the catalytic properties of these materials were evaluated in the DRM process. Results demonstrated that nickel ions favored hydrogen (H2) production over the pristine Li6ZnO4 phase, despite a second H2 production reaction was determined, methane decomposition. Thereby, Li6Zn1-xNixO4 ceramics can be employed as bifunctional materials.

Analysis of sulfur in soil and plant digests using methane as a reaction gas for ICP-MS.

Quantitation of sulfur (S) is vitally important for analysis of agricultural soil and plant samples due to the requirement of S in living organisms. Although inductively coupled plasma mass spectrometry (ICP-MS) is a commonly used and robust instrument for multi-elemental detection, S is usually analysed by ICP-optical emission spectroscopy (OES) since S quantitation poses a particular challenge for ICP-MS due to interferences on all S isotopes. The requirement for analysis by two instruments increases time and cost for sample analysis, hence analysis by one instrument is desirable. The use of reaction gases in ICP-MS can improve the performance by shifting S to a mass for detection where no interference is present. This work explored the potential of methane as a reaction gas for analysis of S in soil and plant samples to give users an alternative option to oxygen. The product ion clusters CH2SH+ were monitored (m/z 47 and 49 on ICP-MS and with mass shift of +15 from Q1 → Q2 using 32 â†’ 47 and 34 â†’ 49 on triple quadrupole ICP-MS). As expected, triple quadrupole ICP-MS performed better than single quadrupole ICP-MS containing a reaction cell due to the ability to preselect the m/z of choice and remove ions that may react with methane in the reaction cell. The method detection limit (MDL) was 150 mg kg-1 S for plants and 53 mg kg-1 S for soils which is fit for requirements. This is the first-time methane has been reported as a reaction gas for analysis of S and shows promising results for agricultural samples when using a triple quadrupole ICP-MS. Results compared well to those obtained via the more commonly used ICP-optical emission spectroscopy (OES) method with results <20 % for all samples. Interlaboratory comparison samples were within 2 Z-scores of the consensus mean. In the absence of ICP-MS/MS, Q-ICP-MS with detection of cluster m/z 47 was deemed to be suitable for detection of S in plant samples, with acceptable MDL (250 mg kg-1 S), acceptable precision (<20 % RSD) and <20 % variation to the reported ICP-OES result.

A Patent Landscape on Methane Oxidizing Bacteria (MOB) or Methanotrophs.

Methane-oxidizing bacteria (MOB) or methanotrophs are a category of bacteria that rely on methane as their primary carbon and energy source. Methane is the second most abundant greenhouse gas after carbon dioxide and is comparatively far more potent in trapping heat in the atmosphere. MOBs are important microorganisms in the global carbon cycle where they play a crucial role in the oxidation of methane. The present review provides a comprehensive patent landscape on technology development using MOB. The first patent in this technology domain was recorded in 1971, with a notable surge in activity observed in 2020. A detailed patent analysis revealed that the early inventions were mainly focused on the production of various metabolites and bioremediation using MOB. In the later years, patents were filed in the area of identification of various species of MOB and their large-scale production. From 2010 onwards, consistent patent filing was observed in the genetic engineering of MOB to enhance their methane oxidizing capacity. The United States and China have emerged as the global leaders in terms of patent filing in this technology space. Precigen Inc. and Exxon Research Engineering Co., US were the top patent assignees followed by the University of Tsinghua and Calysta Inc. The Highest number of patent applications have claimed metabolite production by using MOB followed by their use in bioremediation. Methylosinus has emerged as the predominant microorganism of choice for methane oxidation applications.

Machine Learning Predictions of Methane Storage in MOFs: Diverse Materials, Multiple Operating Conditions, and Reverse Models.

A machine learning (ML) model is developed for predicting useable methane (CH4) capacities in metal-organic frameworks (MOFs). The model applies to a wide variety of MOFs, including those with and without open metal sites, and predicts capacities for multiple pressure swing conditions. Despite its wider applicability, the model requires only 5 measurable structural features as input, yet achieves accuracies that surpass less-general models. Application of the model to a database of more than a million hypothetical MOFs identified several hundred whose capacities surpass that of the benchmark MOF, UMCM-152. Guided by the computational predictions, one of the promising candidates, UMCM-153, was synthesized and demonstrated to achieve superior volumetric capacity for CH4. Feature importance analyses reveal that pore volume and gravimetric surface area are the most important features for predicting CH4 capacity in MOFs. Finally, a reverse ML model is demonstrated. This model predicts the set of elementary MOF structural properties needed to achieve a desired CH4 capacity for a prescribed operating condition.

Methane emission, nitrogen excretion, and energy partitioning in Hanwoo steers fed a typical TMR diet supplemented with Pharbitis nil seeds.

Two in vivo experiments were conducted to evaluate the potential of Pharbitis nil seeds (PA) as an anti-methanogenic additive to ruminant feed. In experiment 1, six Hanwoo steers (459.0 ± 25.8 kg) were fed either a total mixed ration (TMR; 32-d period) or TMR supplemented with PA at 5% dry matter (DM) intake (TMR-PA; 45-d period) for two consecutive periods. Fecal and urine outputs were measured in an apparent digestibility trial in both periods. Methane (CH4) yield and heat energy (HE) were measured using respiratory chambers equipped with gas analyzers. In experiment 2, five rumen cannulated Holstein steers (744 ± 35 kg) were fed the same TMR or TMR-PA diets for 40 days; rumen samples were collected at 0, 1.5, and 3 h after feeding on the last day of the feeding period. In experiment 1, although there were no differences (p > 0.05) in nutrients or gross energy intake (GEI) between the groups, an increase (p < 0.05) in the apparent digestibility of DM (9.1%) and neutral detergent fiber (22.9%) was observed in the TMR-PA fed Hanwoo steers. Pronounced decreases (p < 0.05) in CH4 (g/Kg DM; 17.1%) and urinary N excretion (% N intake; 7.6%) were observed in the TMR-PA group, leading to a 14.7% increase in metabolizable energy intake (% GEI). However, only a numerical increase (p > 0.05) in retained energy was observed due to the increase in HE loss. In experiment 2, a drastic decrease (p < 0.05) in rumen ammonia concentration (56.3%) associated with an increased (p = 0.091) rumen short-chain fatty acid concentration 1.5 h after feeding were observed in TMR-PA fed Holstein steers. A 26.6% increase (p < 0.05) in the propionate proportion during the treatment period clearly reflected a shift in the ruminal H2 sink after 3 h of feeding. A 40% reduction (p = 0.067) in the relative abundance of rumen protozoa Entodinium caudatum was also observed. It was concluded that PA could be a natural feed additive for CH4 and N emission abatement.

Genetic parameters for methane production, intensity, and yield predicted from milk mid-infrared spectra throughout lactation in Holstein dairy cows.

Genetic selection to reduce methane (CH4) emissions is a promising solution for reducing the environmental impact of dairy cattle production. Before such a selection program can be implemented, however, it is necessary to have a better understanding of the genetic determinism of CH4 emissions and how this might influence other traits of interest. In this study, we performed a genetic analysis of 6 CH4 traits predicted from milk mid-infrared spectra. We predicted 4 CH4 traits in g/d (MeP, calculated using different prediction equations), one in g/kg of fat- and protein-corrected milk (MeI), and one in g/kg of dry matter intake (MeY). Using an external data set, we determined these prediction equations to be applicable in the range of 70 to 200 DIM. We then estimated genetic parameters in this DIM range using random regression models on a large data set of 829,025 spectra collected between January 2013 and February 2023 from 167,514 first- and second-parity Holstein cows. The 6 CH4 traits were found to be genetically stable throughout and across lactations, with average genetic correlations within a lactation ranging from 0.93 to 0.98, and those between lactations ranging from 0.92 to 0.98. All 6 CH4 traits were also found to be heritable, with average heritability ranging from 0.24 to 0.45. The average pairwise genetic correlations between the 6 CH4 traits ranged from -0.15 to 0.77, revealing that they are genetically distinct, including the 4 measurements of MeP. Of the 6 traits, 2 measures of MeP and MeI did not present antagonistic genetic correlations with milk yield, fat and protein contents, and SCS, and can probably be included in breeding goals with limited impact on other traits of interest.

The effect of Vachellia eriolaba leaf meal inclusion on growth performance, blood parameters and methane gas emission in lambs fed diets containing ammoniated maize stover.

The study evaluated the effect of Vachellia erioloba leaf meal in diets containing ammoniated maize stove on growth performance, methane emission and heath of growing lambs. Thirty-two female lambs were allocated to the following four dietary treatments: total mixed ration (TMR, control), 20% inclusion of untreated maize stover (UMS), 20% inclusion of ammoniated maize stover (AMS), and combined inclusion of 10% ammoniated maize stover and 10% Vachellia erioloba leaves (AMSVL). Each treatment was replicated 8 times and a lamb in an individual pen was regarded as an experimental unit in a completely randomized design. Feed intake was higher (P < 0.05) in lambs fed the AMS and AMSVL diets compared to those fed UMS. Final body weights were higher in lambs fed the AMS and AMSVL diets. Both average daily gain (ADG) and feed convention ratio (FCR) were not affected by diet. In comparison with the AMS and AMSVL diets, the lambs fed the UMS diet had the highest (P < 0.05) methane emission. Overall, lambs fed the control diets had the lowest (P < 0.05) methane gas emission. Blood hematological values were affected by diet with the AMSVL fed lambs having the highest (P < 0.05) mean platelet volume (MPV) and procalcitonin (PCT) values. Furthermore, total albumin, amylase and total bilirubin were the highest (P < 0.05) in lambs fed on the AMSVL diet. Lambs fed on AMS diet had the highest (P < 0.05) serum urea levels. It can be concluded that combined inclusion of ammoniated maize stover and Vachellia leaves improved feed value and lamb performance when compared to the individual inclusion of both UMS and AMS.

Soil greenhouse gas fluxes partially reduce the net gains in carbon sequestration in mangroves of the Brazilian Amazon.

There is interest in assessing the potential climate mitigation benefit of coastal wetlands based on the balance between their greenhouse gas (GHG) emissions and carbon sequestration. Here we investigated soil GHG fluxes (CO2 and CH4) on mangroves of the Brazilian Amazon coast, and across common land use impacts including shrimp farms and a pasture. We found greater methane fluxes near the Amazon River mouth (1439 to 3312 µg C m-2 h-1), which on average are equivalent to 37% of mangrove C sequestration in the region. Soil CO2 fluxes were predominant in mangrove forests to the East of the Amazon Delta. Land use change shifted mangroves from C sinks (mean sequestration of 12.2 ± 1.4 Mg CO2e ha-1 yr-1) to net GHG sources (mean loss of 8.0 ± 3.3 Mg CO2e ha-1 yr-1). Our data suggests that mangrove forests in the Amazon can aid decreasing the net annual emissions in the Brazilian forest sector in 9.7 ± 0.8 Tg CO2e yr-1 through forest conservation and avoided deforestation.

Low-Temperature Activation and Coupling of Methane on MgO Nanostructures Embedded in Cu2O/Cu(111).

The efficient conversion of methane into valuable hydrocarbons, such as ethane and ethylene, at relatively low temperatures without deactivation issues is crucial for advancing sustainable energy solutions. Herein, AP-XPS and STM studies show that MgO nanostructures (0.2-0.5 nm wide, 0.4-0.6 Šhigh) embedded in a Cu2O/Cu(111) substrate activate methane at room temperature, mainly dissociating it into CHx (x = 2 or 3) and H adatoms, with minimal conversion to C adatoms. These MgO nanostructures in contact with Cu2O/Cu(111) enable C-C coupling into ethane and ethylene at 500 K, a significantly lower temperature than that required for bulk MgO catalysts (>700 K), with negligible carbon deposition and no deactivation. DFT calculations corroborate these experimental findings. The CH4,gas → *CH3 + *H reaction is a downhill process on MgO/Cu2O/Cu(111) surfaces. The activation of methane is facilitated by electron transfer from copper to MgO and the existence of Mg and O atoms with a low coordination number in the oxide nanostructures. The formation of O-CH3 and O-H bonds overcomes the energy necessary for the cleavage of a C-H bond in methane. DFT studies reveal that smaller Mg2O2 model clusters provide stronger binding and lower activation barriers for C-H dissociation in CH4, while larger Mg3O3 clusters promote C-C coupling due to weaker *CH3 binding. All of these results emphasize the importance of size when optimizing the catalytic performance of MgO nanostructures in the selective conversion of methane.

How to simulate dissociative chemisorption of methane on metal surfaces.

The dissociation of methane is not only an important reaction step in catalytic processes, but also of fundamental interest. Dynamical effects during the dissociative chemisorption of methane on metal surfaces cause significant differences in computed reaction rates, compared to what is predicted by typical transition state theory (TST) models. It is clear that for a good understanding of the catalytic activation of methane dynamical simulations are required. In this paper, a general blueprint is provided for performing dynamical simulations of the dissociative chemisorption of methane on metal surfaces, by employing either the quasi-classical trajectory or ring polymer molecular dynamics approach. If the computational setup is constructed with great care-since results can be affected considerably by the setup - chemically accurate predictions are achievable. Although this paper concerns methane dissociation, the provided blueprint is, so far, applicable to the dissociative chemisorption of most molecules.

Application of propionate-producing bacterial consortium in ruminal methanogenesis inhibited environment with bromoethanesulfonate as a methanogen direct inhibitor.

Methane production in ruminants is primarily due to the conversion of metabolic hydrogen (H2), produced during anaerobic microbial fermentation, into methane by ruminal methanogens. While this process plays a crucial role in efficiently disposes of H2, it also contributes to environmental pollution and eliminating methane production in the rumen has proven to be challenging. This study investigates the use of probiotics, specifically propionate-producing bacteria, to redirect accumulated H2 in a methane-mitigated environment. For this objective, we supplemented experimental groups with Lactiplantibacillus plantarum and Megasphaera elsdenii for the reinforced acrylate pathway (RA) and Selenomonas ruminantium and Acidipropionibacterium thoenii for the reinforced succinate pathway (RS), as well as a consortium of all four strains (CB), with the total microbial concentration at 1.0 × 1010 cells/mL. To create a methane-mitigated environment, 2-bromoethanesulfonate (BES) was added to all experimental groups at a dose of 15 mg/0.5 g of feed. BES reduced methane production by 85% in vitro, and the addition of propionate-producing bacteria with BES further decreased methane emission by up to 94% compared with the control (CON) group. Although BES did not affect the alpha diversity of the ruminal bacteriome, it reduced total volatile fatty acid production and altered beta diversity of ruminal bacteriota, indicating microbial metabolic adaptations to H2 accumulation. Despite using different bacterial strains targeting divergent metabolic pathways (RA and RS), a decrease in the dominance of the [Eubacterium] ruminantium group suggesting that both approaches may have a similar modulatory effect. An increase in the relative abundance of Succiniclasticum in the CB group suggests that propionate metabolism is enhanced by the addition of a propionate-producing bacterial consortium. These findings recommend using a consortium of propionate-producing bacteria to manage H2 accumulation by altering the rumen bacteriome, thus mitigating the negative effects of methane reduction strategies.

Does 'net zero' mean zero cows?

A significant share of anthropogenic global warming comes from livestock production. There is debate about whether there can be any role for livestock in a climatically sustainable future; the debate is particularly heated for cows and sheep, largely due to the methane they burp out. However, short-lived gases like methane affect climate in a fundamentally different way than long-lived gases like carbon dioxide. Consequently, climate stabilization does not require zeroing-out cattle herds. But this doesn't mean we can eat our beef and have it (a tolerable climate) too-livestock still contribute to global warming. Preventing or limiting future growth in livestock-related emissions can represent a sensible part of the portfolio of responses to the climate crisis, particularly when carbon dioxide emissions are not on track to reach net zero sufficiently quickly.

Strong Subseasonal Variability of Oxic Methane Production Challenges Methane Budgeting in Freshwater Lakes.

Methane (CH4) accumulation in the well-oxygenated lake epilimnion enhances the diffusive atmospheric CH4 emission. Both lateral transport and in situ oxic methane production (OMP) have been suggested as potential sources. While the latter has been recently supported by increasing evidence, quantifying the exact contribution of OMP to atmospheric emissions remains challenging. Based on a large high-resolution field data set collected during 2019-2020 in the deep stratified Lake Stechlin and on three-dimensional hydrodynamic modeling, we improved existing CH4 budgets by resolving each component of the mass balance model at a seasonal scale and therefore better constrained the residual OMP. All terms in our model showed a large temporal variability at scales from intraday to seasonal, and the modeled OMP was most sensitive to the surface CH4 flux estimates. Future efforts are needed to reduce the uncertainties in estimating OMP rates using the mass balance approach by increasing the frequency of atmospheric CH4 flux measurements.

Selective Electrochemical Conversion of CO2 into Methane on Ag-Decorated Copper Microsphere.

We synthesized the silver-decorated copper microsphere via the hydrothermal method followed by photoreduction of silver ions. Sub 100 nm Ag nanoparticles anchored on the surface of Cu microspheres enhance the electrochemical performance and the selectivity of the CO2 reduction into CH4. Incorporating Ag nanoparticles onto Cu lowers the charge transfer resistance, enhancing the catalyst's conductivity and active site and increasing the rate of CO2 reduction. The faradaic efficiency of silver nanoparticles decorated copper microsphere for methane was 70.94 %, almost twice that of a copper microsphere (44 %). The electrochemical performance showed higher catalytic properties, stability, and faradaic efficiency of silver-decorated copper microspheres.

Do compost-based landfill biocover systems designed for methane oxidation emit nitrous oxide in significant amounts?

Landfills constitute a significant source of methane (CH4), thereby contributing to climate change. CH4 emissions from old and smaller landfills can be mitigated by compost-based biocover systems designed for optimal microbial CH4 oxidation. It is well-known that the strong greenhouse gas nitrous oxide (N2O) is generated during the composting process, which potentially could continue after incorporating compost into the biocover system. Field studies were performed at three full-scale biocover systems established at Danish landfills and included surface screenings, surface flux measurements and gas composition analysis. To assess if N2O generated in the biofilter-compost material would hamper the climate benefit from CH4 oxidised in a biofilter, CH4 removed was compared to N2O generated, with both calculated in CO2-eq. Two assessments were performed. The first considered individual measurement locations on the biocover, whereas the second considered the overall performance of the biocover. By comparing CH4 oxidation rates to the emitted N2O, both approaches showed that there is no risk that N2O emission will negatively affect the CH4 mitigation efficiency of compost-based biocover systems established at landfills. The ratio of N2O emitted to CH4 oxidized (both in unit kg CO2-eq per day) was less than 2.3% for both approaches, and in most cases below 1%.

Glacier melting promotes methane emission via increased methanogenic activity in the foreland alpine meadow.

Annual glacier melting alters hydrothermal conditions of the foreland alpine meadows, and causes significant fluctuations in methane (CH4) flux. Previously we found that Tibetan glacier foreland alpine meadow shifts to CH4 source from sink during the melting season, but the potential mechanisms remain unclear. This study, via combination of in-situ measurement of seasonal CH4 flux and survey of microbial species that may involve in CH4 metabolism, explores the causes of glacier melting on CH4 flux in a glacier foreland alpine meadow on Tibetan Plateau. We determined a pronounced CH4 emission (13.95 µg·m-2·h-1) in August (melting season) but CH4 uptake in June (-3.76 µg·m-2·h-1) and October (-17.77 µg·m-2·h-1), and 1.4-fold higher soil moisture in August than the other two months. This showed a direct correlation of CH4 flux with glacier melting increased soil water. Additionally, glacier melting caused more CH4 fluxes increase in hollows than in hummocks. Amplicon sequencing determined 126-fold higher abundance of mcrA, the methanogenic marker gene, in August than in June and October, and a higher relative abundance of a fungal phylum Mortierellomycota and syntrophic bacteria that convert the fatty acids, the degradation intermediates of organic complexes to CO2 and acetate, the methanogenic substrates like in August. However, no seasonal variation of pmoA, the marker gene of aerobic methanotrophs, was observed. It appears that glacier melting promotes the CH4 producing but not the consuming microorganisms, thus leading to increased CH4 emission. The findings of this work indicate that global warming resulted glacier melting would increase global CH4 emissions, and in turn worsens global warming, so an alarming positive feedback loop.