Low-temperature oxidation of methane mediated by Al-doped ZnO cluster and nanowire: a first-principles investigation.

CONTEXT: First-principles calculations are performed to investigate the catalytic oxidation of methane by using N2O as an oxidizing agent over aluminum (Al)-doped Zn12O12 cluster and (Zn12O12)2 nanowire. The impact of Al impurity on the geometry, electronic structure, and surface reactivity of Zn12O12 and (Zn12O12)2 is thoroughly studied. Our study demonstrates that Al-doped ZnO systems have a better adsorption ability than the corresponding pristine counterparts. It is found that N2O molecule is initially decomposed on the Al site to provide the N2 molecule, and an Al-O intermediate which is an active species for the CH4 oxidation. The conversion of CH4 into CH3OH over AlZn11O12 and (AlZn11O12)2 requires an activation energy of 0.45 and 0.29 eV, respectively, indicating it can be easily performed at normal temperatures. Besides, the overoxidation of methanol into formaldehyde cannot take place over the AlZn11O12 and (AlZn11O12)2, due to the high energy barrier needed to dissociate C-H bond of the CH3O intermediate. METHOD: Dispersion-corrected density functional theory calculations were performed through GGA-PBE exchange-correlation functional combined with a numerical double-ζ plus polarization (DNP) basis set as implemented in DMol3. To include the relativistic effects of core electrons of Zn atoms, DFT-semicore pseudopotentials were adopted. The DFT + D scheme proposed by Grimme was used to involve weak dispersion interactions within the DFT calculations. The reaction energy paths were generated by the minimum energy path calculations using the NEB method.

Microbial mechanisms for CO2 and CH4 emissions in Robinia pseudoacacia forests along a North-South transect in the Loess Plateau.

Forest soil microbes play a crucial role in regulating atmospheric-soil carbon fluxes. Environmental heterogeneity across forest types and regions may lead to differences in soil CO2 and CH4 emissions. However, the microbial mechanisms underlying these emission variations are currently unclear. In this study, we measured CO2 and CH4 emissions of Robinia pseudoacacia forests along a north-south transect in the Loess Plateau. Using metagenomic sequencing, we investigated the structural and functional profiles of soil carbon cycling microbial communities. Results indicated that the forest CO2 emissions of Robinia pseudoacacia was significantly higher in the north region than in the south region, while the CH4 emission was oppositely. This is mainly attributed to changes in gene abundance driven by soil pH and moisture in participating carbon degradation and methane oxidation processes across different forest regions. The gene differences in carbon fixation processes between regions primarily stem from the Calvin cycle, where the abundance of rbcL, rbcS, and prkB genes dominates microbial carbon fixation in forest soils. Random forest models revealed key genes involved in predicting forest soil CO2 emissions, including SGA1 and amyA for starch decomposition, TYR for lignin decomposition, chitinase for chitin decomposition, and pectinesterase for pectin decomposition. Microbial functional characterization revealed that interregional differences in CH4 emissions during methane metabolism may originate from methane oxidation processes, and the associated gene abundances (glyA, ppc, and pmoB) were key genes for predicting CH4 emissions from forest soils. Our results provide new insights into the microbial mechanisms of CO2 and CH4 emissions from forest soils, which will be crucial for accurate prediction of the forest soil carbon cycle in the future.

Molecular simulation of CO2/N2 injection on CH4 adsorption and diffusion.

As an efficient and clean energy, coalbed methane development and utilization have deep significance in promoting energy conservation and emission reduction, reducing greenhouse gas emissions. Therefore, molecular simulation was utilized to study the influence of N2/CO2 on the adsorption and diffusion of methane in coal under different gas injection methods and to elucidate the influence of varying gas injection methods on the efficiency of coalbed methane extraction, which provides a basis for the efficient development of coalbed methane. The results show that the adsorption effect of gases in coal decreases with the increase of temperature and increases with the rise of pressure, and the adsorption performance of the three gases in coal shows the law of CO2 > CH4 > N2. In addition, the injection of CO2/N2 had an obvious inhibition effect on CH4 adsorption, and the inhibition effect of CO2 was more significant, and the inhibition effect on CH4 adsorption reached the maximum when the two gases were mixture injected. In terms of diffusion, compared with separate injection, mixed injection of N2 + CO2 promotes CH4 diffusion more effectively, which can be reflected in the relative concentration distribution and velocity distribution. The injection of N2 helps to increase the porosity of coal, and the injection of CO2 and N2 + CO2 will lead to the decrease of porosity, but the mixed gas injection has less effect than the injection of CO2 alone.

Synchronous reinforcement azo dyes decolorization and anaerobic granular sludge stability by Fe, N co-modified biochar: Enhancement based on extracellular electron transfer.

Anaerobic digestion (AD) treatment of azo dyes wastewater often suffers from low decolorization efficiency and poor stability of anaerobic granular sludge (AnGS). In this study, iron and nitrogen co-modified biochar (FNC) was synthesized based on the secondary calcination method, and the feasibility of this material for enhanced AD treatment of azo dye wastewater and its mechanism were investigated. FNC not only formed richer conducting functional groups, but also generated Fe2+/Fe3+ redox pairs. The decolorization efficiency of Congo red and AD properties (e.g., methane production) were enhanced by FNC. After adding FNC, the content of extracellular polymeric substances (EPS) and the ratio of proteins remained stable under the impact of Congo red, which greatly protected the internal microbial community. This was mainly contributed to the excellent electrochemical properties of FNC, which strengthened the microbial extracellular electron transfer and realized the coupled mechanism of action: On the one hand, an electron transfer bridge between decolorizing bacteria and dyes was constructed to achieve rapid decolorization of azo dyes and mitigate the impact on methanogenic bacteria; On the other hand, the stability of AnGS was enhanced based on enhanced extracellular polymeric substances secretion, microbial community and direct interspecies electron transfer (DIET) process. This study provides a new idea for enhanced AD treatment of azo dyes wastewater.

Methane concentration in the heartwood of living trees in a cold temperate mountain forest: variation, transport and emission.

Forest soils are the largest terrestrial sink of methane, but CH4 produced in tree trunks by methanogenic archaea and emitted into the atmosphere can significantly offset CH4 oxidation in the soil. However, our mechanistic understanding of CH4 accumulation in tree trunks, in relation with CH4 emission from the trunk surface, is still limited. We characterised temporal variations in the molar fraction of CH4 in the heartwood of trees ([CH4]HW) of four different species in a mountain forest and addressed the relationship between [CH4]HW and emission from the surface of the trunk (${F}_{CH_4}$), in connection with the characteristics of the wood. [CH4]HW were measured monthly for 15 months using gas-porous tubes permanently inserted into the trunk. [CH4]HW were above ambient CH4 molar fraction for all trees, lower than 100 ppm for seven trees, higher for the nine other trees and greater than 200,000 ppm (> 20%) for two of these nine trees. [CH4]HW varied monthly but were not primarily determined by trunk temperature. Heartwood diffusive resistance for CH4 was variable between trees, not only due to heartwood characteristics but probably also related to source location. ${F}_{CH_4}$were weakly correlated with [CH4]HW measured a few days after. The resulting apparent diffusion coefficient was also variable between trees suggesting variations in the size and location of the CH4 production sites as well as resistance to gas transport within the trunk. Our results highlight the challenges that must be overcome before CH4 emissions can be simulated at the tree level.

Involvement of the basal forebrain and hippocampus in memory deficits in Parkinson's disease.

INTRODUCTION: Magnetic resonance imaging (MRI)-determined atrophy of the nucleus basalis of Meynert (Ch4) predicts cognitive decline in Parkinson's disease (PD). However, interactions with other brain regions causing the decline remain unclear. This study aimed to describe how MRI-determined Ch4 atrophy leads to cognitive decline in patients with PD. METHODS: We evaluated 137 patients with PD and 39 healthy controls using neuropsychological examinations, MRI, and 123I-ioflupane single-photon emission computed tomography. First, we explored brain areas with regional gray matter loss correlated with Ch4 volume reduction using voxel-based morphometry (VBM). We then assessed the correlation between Ch4 volume reduction and cognitive impairments in PD using partial correlation coefficients (rpar). Finally, we examined whether the regional gray matter loss mediated the association between Ch4 volume reduction and cognitive impairments using mediation analysis. RESULTS: Our PD cohort was "advanced-stage enriched." VBM analyses revealed that Ch4 volume loss was correlated with volume reduction in the medial temporal lobe in PD (P < 0.05, family-wise error corrected, >29 voxels). Ch4 volume reduction was significantly correlated with verbal memory deficits in PD when adjusted for age, sex, total brain volume, and 123I-ioflupane uptake in the caudate (rpar = 0.28, P < 0.001). The mediation analysis revealed that the hippocampus mediated the effects of Ch4 volumes on verbal memory (average causal mediation effect = 0.013, 95 % CI = 0.006-0.020, P < 0.001). CONCLUSION: Particularly in advanced-stage PD, Ch4 atrophy was associated with medial temporal lobe atrophy, which played an intermediary role in the relationship between Ch4 atrophy and verbal memory impairments.

Limosilactobacillus Regulating Microbial Communities to Overcome the Hydrolysis Bottleneck with Efficient One-Step Co-Production of H2 and CH4.

The efficient co-production of H2 and CH4 via anaerobic digestion (AD) requires separate stages, as it cannot yet be achieved in one step. Lactic acid bacteria (LAB) (Limosilactobacillus) release H2 and acetate by enhancing hydrolysis, potentially increasing CH4 production with simultaneous H2 accumulation. This study investigated the enhanced effect of one-step co-production of H2 and CH4 in AD by LAB and elucidated its enhancement mechanisms. The results showed that 236.3 times increase in H2 production and 7.1 times increase in CH4 production are achieved, resulting in profits of 469.39 USD. Model substrates lignocellulosic straw, sodium acetate, and H2 confirmes LAB work on the hydrolysis stage and subsequent sustainable volatile fatty acid production during the first 6 days of AD. In this stage, the enrichment of Limosilactobacillus carrying bglB and xynB, the glycolysis pathway, and the high activity of protease, acetate kinase, and [FeFe] hydrogenase, jointly achieved rapid acetate and H2 accumulation, driving hydrogenotrophic methanogenesis dominated. From day 7 to 24, with enriched Methanosarcina, and increased methenyltetrahydromethanopterin hydrogenase activity, continuously produced acetate led to the mainly acetoclastic methanogenesis shift from hydrogenotrophic methanogenesis. The power generation capacity of LAB-enhanced AD is 333.33 times that of China's 24,000 m3 biogas plant.

The use of infrared thermography as an indicator of methane production in hair sheep.

Infrared thermography may be an alternative technology for measuring the amount of CH4 produced and has the advantages of low cost, speed and efficiency in obtaining results. The study's objective was to determine if the infrared thermography is adequate for predicting the emission of CH4 in hair sheep and the best time after feeding to carry out the measurement. Twelve Santa Inês lambs (females, non-pregnant, with twelve months old and mean body weight of 39.3 ± 2.1 kg) remained for two days in respirometric chambers, in a semi-closed system, to determine the CH4 production. The animals were divided into two treatments, according to the diet provided. During this period, seven thermographic photographs were taken, at times - 1 h, -0.5 h, 0 h, 0.5 h, 1 h, 2 h, 3 h, 5 h, and 7 h, according to the feeding time, defined as 0 h. CH4 production was measured over 24 h. Thermographic images measured the maximum, minimum, average and point temperatures at the left and right flanks. The temperature difference between the left and right flanks (left minus right) was calculated each time. Pearson correlation coefficients, multiple regression and principal component analysis were carried out in SAS®. The best prediction of emission intensity of CH4 (kg of CH4 per dry matter intake) was obtained at 3 h after feeding: CH4/DMI = 13.9016-0,38673 * DifP2 + 3.39089 * DifMed2 (R² = 0.48), using the difference between left and right flanks for point and average temperature measures. Therefore, infrared thermography can be used as an indicator of CH4 production in hair sheep three hours after feeding.

Research Progress in Microporous Materials for Selective Adsorption and Separation of Methane from Low-Grade Gas.

Given that methane (CH4) and nitrogen (N2) have similar properties, achieving high-purity enrichment of CH4 from nitrogen-rich low-grade gas is extremely challenging and is of great significance for sustainable development in energy and the environment. This paper reviews the research progress on carbon-based materials, zeolites, and MOFs as adsorbent materials for CH4/N2 separation. It focuses on the relationship between the composition, pore size, surface chemistry of the adsorbents, CH4/N2 selectivity, and CH4 adsorption capacity. The paper also highlights that controlling pore size and atomic-scale composition and optimizing these features for the best match are key directions for the development of new adsorbents. Additionally, it points out that MOFs, which combine the advantages of carbon-based adsorbents and zeolites, are likely to become the most promising adsorbent materials for efficient CH4/N2 separation.

Sediment properties control riverine methane emissions: A case study of the Liao river in northern China.

River and stream sediments act as biogeochemical reactors for greenhouse gases, particularly methane. However, understanding how riverbed sediment properties influence river carbon emissions remains relatively unclear. The Liao River in northern China is a typical watershed with heterogeneous water and sediment sources, characterized by varying sediment properties. In this study, we surveyed CH4 and CO2 emissions from its mainstem and tributaries during flood and dry seasons. We found consistent seasonal patterns in CH4 and CO2 emissions, with peaks occurring during the flood season. The average CH4 and CO2 fluxes were 1.64 ± 1.80 mmol m-2 d-1 and 59.66 ± 44.60 mmol m-2 d-1, respectively. Notably, the percentage of sediment silt was significantly correlated with CH4 concentration and flux (R2 = 0.12-0.30, p < 0.05). Fine particles dominated the availability of sediment organic matter and redox conditions, which were related to riverine CH4 production and emissions. Structural equation modeling revealed that both grain size and the percentage of TOC (total organic carbon) directly influenced riverine CH4 and CO2 emissions. The organic content and redox conditions of the riverbed sediment collectively explained 65% of riverine CH4 emissions, while grain size composition indirectly controlled CH4 emissions by altering sediment substrate quality and redox conditions. In contrast, river CO2 emissions were only weakly dependent on anaerobic metabolism in riverbed sediments. These findings enhance our understanding of the sources and metabolic mechanisms of riverine CH4 and CO2 emissions and offer potential improvements for estimating carbon fluxes in regional or global riverine networks by considering riverbed sediment properties.

Using ligand regulation, metal replacement, and ligand doping strategies on Zr-FUM to improve methane separation from coalbed gas.

Developing adsorbents suitable for industrial applications that can effectively enhance the separation of methane (CH4) from nitrogen (N2) in coalbed gas is crucial to improve energy recovery and mitigate greenhouse gas emissions. In this study, three modification strategies were implemented on Zr-FUM, including ligand regulation, metal replacement, and ligand doping, to synthesize Zr-FDCA, Al-FUM, and Zr-FUM-FA, with the aim of improving the performance of CH4/N2 separation under humid conditions. The results demonstrated that the promotion of robust orbital overlap and strengthened electrovalent bonding on adsorbents can selectively enhance CH4 adsorption. As a result, Zr-FUM-FA achieved a saturated CH4 adsorption capacity of 1.37 mmol/g, a CH4 working window of 307 s, and a CH4/N2 sorbent selection parameter (Ssp) of 47.31, exceeding the performance of most reported adsorbents. Analyses of the pore structure, surface morphology, and functional groups revealed that the presence of an ultramicropore proximity to CH4, reduced static resistance, and enhanced electrovalent bond were key factors for CH4 separation. Grand Canonical Monte Carlo and Density Functional Theory studies indicated that the introduction of -C-H- in FA played a crucial role in enhancing CH4 adsorption. Optimization of adsorption parameters using the Aspen adsorption package showed that in a dual-adsorbent bed system, the recovery and purity of CH4 in Zr-FUM-FA reach 99.5% and 97.3%, respectively, providing important theoretical support for the improvement of CH4 recovery in the pressure swing adsorption process from coalbed gas.

Methane oxidation driven by multiple electron acceptors in the water level fluctuation zone of the Three Gorges Reservoir area, China.

Water level fluctuations in China's Three Gorges Reservoir (TGR) area are typical of many reservoirs and significantly impact water level fluctuation zones (WLFZ), including upstream rivers. Understanding methane oxidation in the TGR-WLFZ is crucial for evaluating the impact of large-scale reservoir construction on global climate change. In this study, we investigated methane oxidation rates in the TGR-WLFZ, focusing on periods of drying and flooding. The highest methane oxidation rates were observed during the drying period, ranging from 35.69 to 56.32 nmol/(g soil)/d, while the lowest rates were recorded during the flooding period, at 11.58 to 11.98 nmol/(g soil)/d, in lab-scale simulated columns. Using 13CH4 labeling experiments, we measured CH4 oxidation potentials for aerobic methane oxidation (AMO) using oxygen and anaerobic oxidation of methane (AOM) using nitrite, nitrate, sulfate, ferric iron, and manganese oxide as electron acceptors at varying concentrations. AMO was the dominant process across all experiments, with potentials ranging from 145.71 to 180.77 nmol 13CO2/(g soil)/d. For AOM, metal-dependent oxidation, particularly with Fe (III) and Mn(IV), was predominant (12.64-17.59 and 3.91-12.69 nmol 13CO2/(g soil)/d, respectively), followed by nitrite and nitrate-dependent pathways (1.49-9.10 nmol 13CO2/(g soil)/d). Sulfate-dependent AOM was limited (1.33-3.27 nmol 13CO2/(g soil)/d). Metagenomic analysis identified key microorganisms responsible for AMO, such as unclassified_f_Methylobacteriaeae and Methylobacterium sp., and for AOM are Ca. Methylomirabilis oxyfera, Ca. Methanoperedens nitroreducens and Ca. Methylomirabilis sp. Complete functional genes and enzymes for the methane oxidation and reverse methanogenesis pathways were obtained in each hydrological period, with the highest content during the drying period and the lowest during flooding. Our study shows that reservoirs, traditionally considered significant sources of methane, may also act as methane sinks. This finding raises new questions: How do different methane oxidation pathways respond to water level fluctuations in reservoirs, and are some pathways more resilient to changes in hydrological conditions?

Arsenic Reduces Methane Emissions from Paddy Soils: Insights from Continental Investigation and Laboratory Incubations.

Arsenic (As) contamination and methane (CH4) emissions co-occur in rice paddies. However, how As impacts CH4 production, oxidation, and emission dynamics is unknown. Here, we investigated the abundances and activities of CH4-cycling microbes from 132 paddy soils with different As concentrations across continental China using metagenomics and the reverse transcription polymerase chain reaction. Our results revealed that As was a crucial factor affecting the abundance and distribution patterns of the mcrA gene, which is responsible for CH4 production and anaerobic CH4 oxidation. Laboratory incubation experiments showed that adding 30 mg kg-1 arsenate increased 13CO2 production by 10-fold, ultimately decreasing CH4 emissions by 68.5%. The inhibition of CH4 emissions by As was induced through three aspects: (1) the toxicity of As decreased the abundance and activity of the methanogens; (2) the adaptability and response of methanotrophs to As is beneficial for CH4 oxidation under As stress; and (3) the more robust arsenate reduction would anaerobically consume more CH4 in paddies. Additionally, significant positive correlations were observed between arsC and pmoA gene abundance in both the observational study and incubation experiment. These findings enhance our understanding of the mechanisms underlying the interactions between As and CH4 cycling in soils.

Hydroxyl-Functionalized Polymers of Intrinsic Microporosity and Dual-Functionalized Blends for High-Performance Membrane-Based Gas Separations.

Membrane technology has shown significant growth during the past two decades in the gas separation industry due to its energy-savings, compact and modular design, continuous operation, and environmentally benign nature. Robust materials with higher permeability and selectivity are key to reduce capital and operational cost, pushing it forward to replace or debottleneck conventional energy-intensive unit operations such as distillation. Recently designed ladder polymers of intrinsic microporosity (PIM) and polyimides of intrinsic microporosity (PIM-PI) with pores <20 Å have demonstrated excellent gas permeation performance. Here, a series of plasticization-resistant PIM-based membrane materials is reported, including the first example of a hydroxyl-functionalized triptycene- and Tröger's base-derived ladder PIM and two PIM-PI homopolymers and a series of dual-functionalized polyimide blends containing hydroxyl- and carboxyl-functionalized groups. Specifically, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)-based PIM-PI blends demonstrated extremely high selectivity for a variety of industrially important applications. An optimized polyimide blend containing ─OH and ─COOH groups showed permselectivity values of 136 for CO2/CH4, 11.4 for O2/N2 and 636 for H2/CH4. Such extreme size-sieving capabilities are attributed to physical crosslinking induced by strong hydrogen bonding forming tightly structured polymer networks. The study provides a new general strategy for developing plasticization resistant, robust, and highly-selective PIM-based membrane materials.

Molecular Insight into the Electric Field Regulation of N2 and CH4 Adsorption in the Trapdoor ZSM-25 Zeolites.

Controlling gas admission by regulating pore accessibility in porous materials has been a topic of extensive research. Recently, the electric field (E-field) has emerged as an external stimulus to alter the adsorption behavior of some microporous adsorbents. However, the mechanism behind this phenomenon is not yet fully understood. Here, we demonstrate the crucial role of the trapdoor cations of zeolite molecular sieves in E-field-regulated gas adsorption. The E-field activation caused framework expansion and cation deviation, significantly reducing the energy barrier for gas molecules passing through the pore aperture gated by the trapdoor cation. This led to an increase in the N2 adsorption capacity of ZSM-25 and a 60% improvement in N2/CH4 selectivity in the quest for nitrogen rejection for natural gas processing. By combining experimental and computational approaches, we elucidated the influence of E-field activation as a concurrent effect of the reduced heat of adsorption caused by framework expansion and the decrease in the energy barrier resulting from promoted cation oscillation. These findings pave the way for the material design of E-field-regulated adsorption and its application in molecular separation.

Methane oxidation coupling with heavy metal and microplastic transformations for biochar-mediated landfill cover soil.

The impact of co-occurring heavy metal (HM) and microplastic (MP) pollution on methane (CH4) oxidation by methanotrophs (MOB) in landfill cover soil (LCS) and the role of biochar in mediating these collaborative transformations remains unclear. This study conducted batch-scale experiments using LCS treated with individual or combined HMs and MPs, with or without biochar amendment. Differentiation in methanotrophic activities, HM transformations, MP aging, soil properties, microbial communities, and functional genes across the groups were analyzed. Biochar proved essential in sustaining efficient CH4 oxidation under HM and MP stress, mainly by diversifying MOB, and enhancing polysaccharide secretion to mitigate environmental stress. While low levels of HMs slightly inhibited CH4 oxidation, high HM concentration enhanced methanotrophic activities by promoting electron transfer process. MPs consistently stimulated CH4 oxidation, exerting a stronger influence than HMs. Notably, the simultaneous presence of low levels of HMs and MPs synergistically boosted CH4 oxidation, linked to distinct microbial evolution and adaptation. Methanotrophic activities were demonstrated to affect the fate of HMs and MPs. Complete passivation of Cu was readily achieved, whereas Zn stabilization was negatively influenced by biochar and MPs. The aging of MPs was also partially suppressed by biochar and HM adsorption.

Photocatalytic methane oxidation over a TiO2/SiNWs p-n junction catalyst at room temperature.

Rapid recombination of charge carriers in semiconductors is a main drawback for photocatalytic oxidative coupling of methane (OCM) reactions. Herein, we propose a novel catalyst by developing a p-n junction titania-silicon nanowires (TiO2/SiNWs) heterostructure. The structure is fabricated by atomic layer deposition of TiO2 on p-type SiNWs. The TiO2/SiNWs heterostructure exhibited an outstanding OCM performance under simulated solar light irradiation compared to the single components. This enhanced efficiency was attributed to the intrinsic electrical field formed between n-type TiO2 and p-type SiNWs, which forces generated charge carriers to move in opposite directions and suppresses charge recombination. Besides, surface morphology and optical properties of the the p-n TiO2/SiNWs catalyst are also beneficial for the photocatalytic activity. It is expected that the results of this study will provide massive guidance in synthesizing an efficient photocatalyst for CH4 conversion under mild conditions.

Efficient In/SSZ-39 catalysts for the selective catalytic reduction of NO with CH4.

The M/SSZ-39 catalysts (M = In, Co, Cu, Fe) with different metal species and metal loadings were synthesized using the wet impregnation method on a small-pore SSZ-39 molecular sieve. X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-dehydrogenation and hydrogen temperature program reduction (H2-TPR) were employed to characterize the effects of various metal components and metal loadings on the performance of CH4 selective catalytic reduction of NO reaction (CH4-SCR). The characterization results showed that the In/SSZ-39 catalyst exhibited significantly higher catalytic activity compared to the Cu-, Co-, and Fe/SSZ-39 catalysts, suggesting that indium (In) is a more suitable active ingredient for the CH4-SCR reaction. The xIn/SSZ-39 (x = 1, 2, 3, x represents the In loadings of 1.0 wt%, 2.0 wt% and 3.0 wt%) catalysts, with different In loadings, all present excellent CH4-SCR performance. By varying the In loadings, the type of In species present in the catalyst can be regulated, thus enhancing DeNOx activity and CH4 selectivity in the CH4-SCR reaction. At a low temperature of 400 °C and a low CH4/NO feed ratio (CH4/NO = 1), the 3In/SSZ-39 catalyst, featuring highly active InOx clusters, achieves the best low-temperature CH4-SCR performance, with a high NO conversion rate of up to 90% and a CH4 selectivity of up to 74.2%.

[Research Progress on Production and Emission of CH4 and N2O from Urban Rivers].

Methane （CH4） and nitrous oxide （N2O） are concerning greenhouse gases. Urban rivers have been important emission sources of CH4 and N2O in recent years. It is meaningful for city greenhouse gas reduction to provide a systematic analysis of spatiotemporal characteristics, mechanisms, and influencing factors of the production and emission of CH4 and N2O from urban rivers. This study combed measured data of urban river CH4 and N2O dissolution concentrations and emission fluxes from related literature published in the past 20 years and also concluded the spatiotemporal characteristics of urban river CH4 and N2O emissions. This study estimated that CH4 and N2O emissions （expressed by CO2-eq） from urban rivers in Beijing were 234.63 and 59.53 Gg CO2-eq in 2018, whereas CH4 and N2O emissions （expressed by CO2-eq） from urban rivers in Shanghai were 159.86 and 260.24 Gg CO2-eq in 2018, respectively. These results demonstrated that urban rivers have become important CH4 and N2O emission sources. This study summarized the production/consumption processes and import/export pathways of CH4 and N2O in urban rivers. What is more, this study discussed the main influencing factors of urban river CH4 and N2O production and emissions from the perspectives of river environmental conditions and urbanization effects. At last, the present work prospected the future research trends of urban river CH4 and N2O emissions and provides urban rivers with scientific support for greenhouse gas reduction.

Methane dynamics altered by reservoir operations in a typical tributary of the Three Gorges Reservoir.

Substantial nutrient inputs from reservoir impoundment typically increase sedimentation rate and primary production. This can greatly enhance methane (CH4) production, making reservoirs potentially significant sources of atmospheric CH4. Consequently, elucidating CH4 emissions from reservoirs is crucial for assessing their role in the global methane budget. Reservoir operations can also influence hydrodynamic and biogeochemical processes, potentially leading to pronounced spatiotemporal heterogeneity, especially in reservoirs with complex tributaries, such as the Three Gorges Reservoir (TGR). Although several studies have investigated the spatial and temporal variations in CH4 emissions in the TGR and its tributaries, considerable uncertainties remain regarding the impact of reservoir operations on CH4 dynamics. These uncertainties primarily arise from the limited spatial and temporal resolutions of previous measurements and the complex underlying mechanisms of CH4 dynamics in reservoirs. In this study, we employed a fast-response automated gas equilibrator to measure the spatial distribution and seasonal variations of dissolved CH4 concentrations in XXB, a representative area significantly impacted by TGR operations and known for severe algal blooms. Additionally, we measured CH4 production rates in sediments and diffusive CH4 flux in the surface water. Our multiple campaigns suggest substantial spatial and temporal variability in CH4 concentrations across XXB. Specifically, dissolved CH4 concentrations were generally higher upstream than downstream and exhibited a vertical stratification, with greater concentrations in bottom water compared to surface water. The peak dissolved CH4 concentration was observed in May during the drained period. Our results suggest that the interplay between aquatic organic matter, which promotes CH4 production, and the dilution process caused by intrusion flows from the mainstream primarily drives this spatiotemporal variability. Importantly, our study indicates the feasibility of using strategic reservoir operations to regulate these factors and mitigate CH4 emissions. This eco-environmental approach could also be a pivotal management strategy to reduce greenhouse gas emissions from other reservoirs.