Methane Production Is More Sensitive to Temperature Increase than Aerobic and Anaerobic Methane Oxidation in Chinese Paddy Soils.

Methane emissions from paddy fields can increase under future warming scenarios. Nevertheless, a comprehensive comparison of the temperature sensitivity of methane-related microbial processes remains elusive. Here, we revealed that the temperature sensitivity of methane production (activation energy (Ea) = 0.94 eV; 95% confidence interval (CI), 0.78-1.10 eV) and aerobic (Ea = 0.49 eV; 95% CI, 0.34-0.65 eV) and anaerobic (Ea = 0.46 eV; 95% CI, 0.30-0.62 eV) methane oxidation exhibited notable spatial heterogeneity across 12 Chinese paddy fields spanning 35° longitude and 18° latitude. In addition, the Ea values of aerobic and anaerobic methane oxidation were significantly positively and negatively correlated to the latitude, respectively, while there was no significant correlation between the Ea of methane production and the latitude. Overall, there were no soil factors that had a significant effect on the Ea of methane production. The Ea of aerobic methane oxidation was primarily influenced by the contents of ammonium and clay, whereas the Ea of anaerobic methane oxidation was mainly influenced by the conductivity. Despite the variation, the overall temperature sensitivity of methane production was significantly higher than that of oxidation at a continental scale; therefore, an increase in the emission of methane from paddy fields will be predicted under future warming. Taken together, our study revealed the characteristics of temperature sensitivity of methane production and aerobic and anaerobic methane oxidation simultaneously in Chinese paddy fields, highlighting the potential roles of soil factors in influencing temperature sensitivity.

Highly Selective Synthesis of Acetic Acid from Hydroxyl-Mediated Oxidation of Methane at Low Temperatures.

Direct methane conversion and, in particular, the aerobic oxidation to acetic acid, remain an eminent challenge. Here, we reported a zeolite-supported Au-Fe catalyst (Au-Fe/ZSM-5) that converted methane to acetic acid with molecular oxygen as an oxidant in the presence of CO. Specifically, Au nanoparticles catalyzed the formation of hydroxyl species from the reaction of CO, O2, and H2O, meanwhile ZSM-5-supported atomically dispersed Fe species were responsible for the hydroxyl-mediated coupling of CH4 and CO to generate acetic acid. The reaction over 50 mg of Au-Fe/ZSM-5 under 62 bar (CH4: CO: O2 = 14: 14: 3) at 120 °C for 3.0 h yielded 5.7 millimoles of acetic acid per gram of the catalyst (mmol gcat-1) with the selectivity of 92%, outperformed most of reported catalysts. Significantly, the catalyst remained active even at 60 °C. We anticipate that this hydroxyl-mediated route may guide the design of optimized catalysts for the direct methane functionalization at low temperatures.

Intermittent aeration mitigating carbon emission from landfills with gas-water joint regulation.

Landfill is a significant source of atmospheric CH4 and CO2 emissions. In this study, four landfill reactor systems were constructed to investigate the effects of different ventilation methods, including continuous aeration (20 h d-1) and intermittent aeration (continuous aeration for 4 h d-1 and 2 h of aeration every 12 h, twice a day), on properties of landfilled waste and emissions of CH4 and CO2, in comparison to a traditional landfill. Compared with continuous aeration, intermittent aeration could reduce the potential global warming effect of the CH4 and CO2 emissions, especially multiple intermittent aeration. The CH4 and CO2 emissions could be predicted by the multiple linear regression model based on the contents of carbon, sulfur and/or pH during landfill stabilization. Both intermittent and continuous aeration could enhance the methane oxidation activity of landfilled waste. The aerobic methane oxidation activity of landfilled waste reached the maximums of 50.77-73.78 µg g-1 h-1 after aeration for 5 or 15 d, which was higher than the anaerobic methane oxidation activity (0.45-1.27 µg g-1 h-1). CO2 was the predominant form of organic carbon loss in the bioreactor landfills. Candidatus Methylomirabilis, Methylobacter, Methylomonas and Crenothrix were the main methane-oxidating microorganisms (MOM) in the landfills. Total, NO2--N, pH and Fe3+ were the main environmental variables influencing the MOM community, among which NO2--N and pH had the significant impact on the MOM community. Partial least squares path modelling indicated that aeration modes mainly influenced the emissions of CH4 and CO2 by affecting the degradation of landfilled waste, environmental variables and microbial activities. The results would be helpful for designing aeration systems to reduce the emissions of CH4 and CO2, and the cost during landfill stabilization.

Tidal control on aerobic methane oxidation and mitigation of methane emissions from coastal mangrove sediments.

Mangrove forests represent important sources of methane, partly thwarting their ecosystem function as an efficient atmospheric carbon dioxide sink. Many studies have focused on the spatial and temporal variability of methane emissions from mangrove ecosystems, yet little is known about the microbial and physical controls on the release of biogenic methane from tidally influenced mangrove sediments. Here, we show that aerobic methane oxidation is a key microbial process that effectively reduces methane emissions from mangrove sediments. We further demonstrate clear links between the tidal cycle and fluctuations in methane fluxes, with contrasting methane emission rates under different tidal amplitudes. Our data suggest that both the microbial methane oxidation activity and pressure-induced advective transport modulated methane fluxes in the mangrove sediments. Methane oxidation activity is limited by the availability of oxygen in the surface sediments, which in turn is controlled by tidal dynamics, further highlighting the interactive physico-biogeochemical controls on biological methane fluxes. Although we found some molecular evidence for anaerobic methanotrophs in the deeper sediments, anaerobic methane oxidation seems to play only a minor role in the mangrove sediments, with potential rates being two orders of magnitude lower than those of aerobic methane oxidation. Our findings confirmed the importance of surface sediments as biological barrier for methane. Specifically, when sediments were exposed to the air, methane consumption increased by ∼227%, and the methane flux was reduced by ∼62%, compared to inundated conditions. Our data demonstrate how tides can orchestrate the daily rhythm of methane consumption and production within mangrove sediments, thus explaining the temporal variability of methane emissions in the tidally influenced coastal mangrove systems.

Impacts of O2:CH4 ratios and CH4 concentrations on the denitrification and CH4 oxidations of a novel AME-AD system.

Aerobic methane (CH4) oxidation coupled to denitrification (AME-D) is a promising process for the denitrification of low C/N wastewater. Compared with anaerobic denitrifying bacteria, aerobic denitrifying bacteria may enable AME-D have high denitrification ability under aerobic conditions. This study constructed a novel aerobic methane oxidation coupled to aerobic denitrification (AME-AD) system using the typical aerobic denitrifying bacteria Paracoccus pantotrophus ATCC35512 and the typical aerobic methane oxidizing bacteria Methylosinus trichosporium OB3b. The denitrification and CH4 oxidations of AME-AD with different O2:CH4 ratios (0:1, 0.25:1, 0.5:1, 0.75:1, 1:1 and 1.25:1) and CH4 concentrations (0, 14000, 28000, 42000, 56000 and 70000 mg m-3) were investigated in batch experiments. Higher O2:CH4 ratios can significantly improve the denitrification and CH4 oxidations of the AME-AD (P < 0.05). The treatment with an O2:CH4 ratio of 1.25:1 had the highest denitrification rate (0.036 mg h-1) and highest CH4 oxidation rate (0.20 mg h-1). The CH4 concentration in the headspace was positively correlated with the AME-AD denitrification rate. The calculated CH4/NO3-(mol/mol) in most treatments ranged from 5.76 to 6.84. In addition, excessively high O2 and CH4 concentrations can lead to increased nitrous oxide (N2O) production in AME-AD. The N2O production rate was up to 1.00 µg h-1 when the O2:CH4 was 1.25:1. These results can provide data support for the application of AME-AD for low-C/N wastewater treatment and greenhouse gas emission reduction.

Environmental determinants of aerobic methane oxidation in a tropical river network.

Aerobic methane oxidation (MOX) significantly reduces methane (CH4) emissions from inland water bodies and is, therefore, an important determinant of global CH4 budget. Yet, the magnitude and controls of MOX rates in rivers - a quantitatively significant natural source of atmospheric CH4 - are poorly constrained. Here, we conducted a series of incubation experiments to understand the magnitude and environmental controls of MOX rates in tropical fluvial systems. We observed a large variability in MOX rate (0.03 - 3.45 µmol l-1d-1) shaped by a suit of environmental variables. Accordingly, we developed an empirical model for MOX that incorporate key environmental drivers, including temperature, CH4, total phosphorus, and dissolved oxygen (O2) concentrations, based on the results of our incubation experiments. We show that temperature dependency of MOX (activation energy: 0.66 ± 0.18 eV) is lower than that of sediment methanogenesis (0.71 ± 0.21 eV) in the studied tropical fluvial network. Furthermore, we observed a non-linear relationship between O2 concentration and MOX, with the highest MOX rate occuring ∼135 µmol O2l-1, above or below this "optimal O2" concentration, MOX rate shows a gradual decline. Together, our results suggest that the relatively lower temperature response of MOX compared to methanogenesis along with the projected decrease of O2 concentration due to organic pollution may cause elevated CH4 emission from tropical southeast Asian rivers. Since estimation of CH4 oxidation is often neglected in routine CH4 monitoring programs, the model developed here may help to integrate MOX rate into process-based models for fluvial CH4 budget.

Quasi-homogeneous photoelectrochemical organic transformations for tunable products and 100% conversion ratio.

Photoelectrochemical (PEC) organic transformation at the anode coupled with cathodic H2 generation is a potentially rewarding strategy for efficient solar energy utilization. Nevertheless, achieving the full conversion of organic substrates with exceptional product selectivity remains a formidable hurdle in the context of heterogeneous catalysis at the solid/liquid interface. Here, we put forward a quasi-homogeneous catalysis concept by using the reactive oxygen species (ROS), such as ·OH, H2O2 and SO4•-, as a charge transfer mediator instead of direct heterogeneous catalysis at the solid/liquid interface. In the context of glycerol oxidation, all ROS exhibited a preference for first-order reaction kinetics. These ROS, however, showcased distinct oxidation mechanisms, offering a range of advantages such as âˆ¼ 100 % conversion ratios and the flexibility to tune the resulting products. Glycerol oxidative formic acid with Faradaic efficiency (FE) of 81.2 % was realized by the H2O2 and ·OH, while SO4•- was preferably for glycerol conversion to C3 products like glyceraldehyde and dihydroxyacetone with a total FE of about 80 %. Strikingly, the oxidative coupling of methane to ethanol was successfully achieved in our quasi-homogeneous system, yielding a remarkable production rate of 12.27 µmol h-1 and an impressive selectivity of 92.7 %. This study is anticipated to pave the way for novel approaches in steering solar-driven organic conversions by manipulating ROS to attain desired products and conversion ratios.

Evaluating the efficacy of biogeochemical cover system in mitigating landfill gas emissions: A large-scale laboratory simulation.

Municipal solid waste (MSW) landfills are a significant source of methane (CH4) emissions in the United States, contributing to global warming. Current landfill gas (LFG) management methods, like the landfill cover system and LFG collection system, do not entirely prevent LFG release. Biocovers have the potential to reduce CH4 emissions through microbial oxidation. However, LFG also contains carbon dioxide (CO2) and trace hydrogen sulfide (H2S) depending on waste composition, temperature, moisture content, and age of waste. An innovative biogeochemical cover (BGCC) was developed to tackle these concerns. This cover comprises a biochar-based biocover layer overlaid with a basic oxygen furnace (BOF) steel slag layer. The biochar-based biocover layer oxidizes CH4 emissions, while the BOF slag layer reduces CO2 and H2S through carbonation and sulfidation reaction mechanisms. The BGCC system's field performance remains unexamined. Therefore, a large-scale tank setup simulating near-field conditions was developed to evaluate the BGCC system's ability to mitigate CH4, CO2, and H2S from LFG simultaneously. Synthetic LFG was passed through the BGCC in five distinct phases, each designed to simulate the varying gas compositions and flux rates typical of MSW landfill. Gas profiles along the depth were monitored during each phase, and gas removal efficiency was measured. After testing, biocover and BOF slag samples were extracted to analyze physico-chemical properties. Batch tests were also conducted on samples extracted from the biocover and BOF slag layers to determine potential CH4 oxidation rates and residual CO2 sequestration capacity. The results showed that the BGCC system's CH4 removal efficiency decreased with higher CH4 flux rates, achieving its highest removal (74.7-79.7%) at moderate influx rates (23.9-25.5 g CH4/m2-day) and reducing to its lowest removal (27.4%) at the highest influx rate (57.5 g CH4/m2-day). Complete H2S removal occurred during Phase 3 in the biocover layer of BGCC system. CH4 oxidation rates were highest near the upper (277.9 µg CH4/g-day) and lowest in the deeper region of the biocover layer. In the tank experiment, CO2 breakthrough occurred after 156 days due to drying of the BOF slag layer, with an average residual carbonation capacity of 46 gCO2/kg slag after moisture adjustment. Overall, the BGCC system effectively mitigated LFG emissions, including CH4, CO2, and H2S, at moderate flux rates, showing promise as a comprehensive solution for LFG management.

Exploring modes of microbial interactions with implications for methane cycling.

Methanotrophs are the sole biological sink of methane. Volatile organic compounds (VOCs) produced by heterotrophic bacteria have been demonstrated to be a potential modulating factor of methane consumption. Here, we identify and disentangle the impact of the volatolome of heterotrophic bacteria on the methanotroph activity and proteome, using Methylomonas as model organism. Our study unambiguously shows how methanotrophy can be influenced by other organisms without direct physical contact. This influence is mediated by VOCs (e.g. dimethyl-polysulphides) or/and CO2 emitted during respiration, which can inhibit growth and methane uptake of the methanotroph, while other VOCs had a stimulating effect on methanotroph activity. Depending on whether the methanotroph was exposed to the volatolome of the heterotroph or to CO2, proteomics revealed differential protein expression patterns with the soluble methane monooxygenase being the most affected enzyme. The interaction between methanotrophs and heterotrophs can have strong positive or negative effects on methane consumption, depending on the species interacting with the methanotroph. We identified potential VOCs involved in the inhibition while positive effects may be triggered by CO2 released by heterotrophic respiration. Our experimental proof of methanotroph-heterotroph interactions clearly calls for detailed research into strategies on how to mitigate methane emissions.

Novel, active, and uncultured hydrocarbon-degrading microbes in the ocean.

Given the vast quantity of oil and gas input to the marine environment annually, hydrocarbon degradation by marine microorganisms is an essential ecosystem service. Linkages between taxonomy and hydrocarbon degradation capabilities are largely based on cultivation studies, leaving a knowledge gap regarding the intrinsic ability of uncultured marine microbes to degrade hydrocarbons. To address this knowledge gap, metagenomic sequence data from the Deepwater Horizon (DWH) oil spill deep-sea plume was assembled to which metagenomic and metatranscriptomic reads were mapped. Assembly and binning produced new DWH metagenome-assembled genomes that were evaluated along with their close relatives, all of which are from the marine environment (38 total). These analyses revealed globally distributed hydrocarbon-degrading microbes with clade-specific substrate degradation potentials that have not been reported previously. For example, methane oxidation capabilities were identified in all Cycloclasticus. Furthermore, all Bermanella encoded and expressed genes for non-gaseous n-alkane degradation; however, DWH Bermanella encoded alkane hydroxylase, not alkane 1-monooxygenase. All but one previously unrecognized DWH plume member in the SAR324 and UBA11654 have the capacity for aromatic hydrocarbon degradation. In contrast, Colwellia were diverse in the hydrocarbon substrates they could degrade. All clades encoded nutrient acquisition strategies and response to cold temperatures, while sensory and acquisition capabilities were clade specific. These novel insights regarding hydrocarbon degradation by uncultured planktonic microbes provides missing data, allowing for better prediction of the fate of oil and gas when hydrocarbons are input to the ocean, leading to a greater understanding of the ecological consequences to the marine environment.IMPORTANCEMicrobial degradation of hydrocarbons is a critically important process promoting ecosystem health, yet much of what is known about this process is based on physiological experiments with a few hydrocarbon substrates and cultured microbes. Thus, the ability to degrade the diversity of hydrocarbons that comprise oil and gas by microbes in the environment, particularly in the ocean, is not well characterized. Therefore, this study aimed to utilize non-cultivation-based 'omics data to explore novel genomes of uncultured marine microbes involved in degradation of oil and gas. Analyses of newly assembled metagenomic data and previously existing genomes from other marine data sets, with metagenomic and metatranscriptomic read recruitment, revealed globally distributed hydrocarbon-degrading marine microbes with clade-specific substrate degradation potentials that have not been previously reported. This new understanding of oil and gas degradation by uncultured marine microbes suggested that the global ocean harbors a diversity of hydrocarbon-degrading bacteria, which can act as primary agents regulating ecosystem health.

Methane-Driven Perchlorate Reduction by a Microbial Consortium.

The phenomenon of methane oxidation linked to perchlorate reduction has been reported in multiple studies; yet, the underlying microbial mechanisms remain unclear. Here, we enriched suspended cultures by performing methane-driven perchlorate reduction under oxygen-limiting conditions in a membrane bioreactor (MBR). Batch test results proved that perchlorate reduction was coupled to methane oxidation, in which acetate was predicted as the potential intermediate and oxygen played an essential role in activating methane. By combining DNA-based stable isotope probing incubation and high-throughput sequencing analyses of 16S rRNA gene and functional genes (pmoA, pcrA, and narG), we found that synergistic interactions between aerobic methanotrophs (Methylococcus and Methylocystis) and perchlorate-reducing bacteria (PRB; Denitratisoma and Dechloromonas) played active roles in mediating methane-driven perchlorate reduction. This partnership was further demonstrated by coculture experiments in which the aerobic methanotroph could produce acetate to support PRB to complete perchlorate reduction. Our findings advance the understanding of the methane-driven perchlorate reduction process and have implications for similar microbial consortia linking methane and chlorine biogeochemical cycles in natural environments.

Spatial variation of methane oxidation and carbon dioxide sequestration in landfill biogeochemical cover.

The study investigated the spatial variation of potential methane (CH4) oxidation and residual carbon dioxide (CO2) sequestration in biogeochemical cover (BGCC) system designed to remove CH4, CO2, and hydrogen sulfide (H2S) from landfill gas (LFG) emissions. A 50 cm x 50 cm x 100 cm tank simulated BGCC system, comprising a biochar-amended soil (BAS) layer for CH4 oxidation, a basic oxygen furnace (BOF) slag layer for CO2 and H2S sequestration, and an upper topsoil layer. Synthetic LFG was flushed through the system in five phases, with each corresponding to different compositions and flow rates. Following monitoring, the system was dismantled, and samples were extracted from different depths and locations to analyze spatial variations, focusing on moisture content (MC), organic content (OC), pH, and electrical conductivity (EC). Additionally, batch tests on selected samples from BAS and BOF slag layers were performed to assess potential CH4 oxidation and residual carbonation capacity. The aim of study was to evaluate the BGCC's effectiveness in LFG mitigation, however this study focused on assessing spatial variations in physico-chemical properties, CH4 oxidation in the BAS layer, and residual carbonation in the BOF slag layer. Findings revealed CH4 oxidation in the BAS layer varied between 22.4 and 277.9 µg CH4/g-day, with higher rates in the upper part, and significant spatial variations at 50 cm below ground surface (bgs) compared to 85 cm bgs. The BOF slag layer showed a residual carbonation capacity of 40-49.3 g CO2/kg slag, indicating non-uniform carbonation. Overall, CH4 oxidation and CO2 sequestration capacities varied spatially and with depth in the BGCC system.

Loss of microbial diversity increases methane emissions and arsenic release in paddy soils.

Microorganisms are vital to the emission of greenhouse gases and transforming pollutants in paddy soils. However, the impact of microbial diversity loss on anaerobic methane (CH4) oxidation and arsenic (As) reduction under flooded conditions remains unclear. In this study, we inoculated microbial suspensions into natural As-contaminated paddy soils using a dilution approach (untreated, 10-2, 10-4, 10-6, 10-8 dilutions) to manipulate microbial diversity levels. The results revealed that the 10-4 and 10-6 dilutions resulted in the highest CH4 emissions (97.0 µmol and 102.3 µmol) compared to untreated groups (27.6 µmol). However, anaerobic CH4 oxidation was not observed in 10-4 dilution groups and higher dilutions, suggesting the loss of diversity inhibited the natural reduction of CH4. Moreover, the porewater As concentration in the dilution groups was 1.8-8.2 times greater than in the untreated groups. The loss of microbial diversity promoted the reductive dissolution of iron (Fe) minerals bearing As, leading to increased concentrations of Fe(II) and dissolved organic carbon (DOC), which further enhanced As release (Fe(II), R = 0.9, p < 0.001) (DOC, R = 0.8, p < 0.001) from soil to porewater. However, CH4-dependent As(V) reduction was almost entirely inhibited under diversity loss. The decline in microbial diversity increased the relative abundances of methanogens (e.g., Methanobacterium and Methanomassiliicoccus), Fe(III)/As(V)-reducing bacteria (e.g., Bacillus, Clostridium_sensu_stricto_10, and Geobacter), and the related functional genes (i.e., mcrA and Geo). These findings suggest that microbial diversity is critical for specialized soil processes, highlighting the detrimental effects of biodiversity loss on CH4 emissions and As release in As-contaminated paddies.

Long-term observations on the hydraulic performance of a combined capillary barrier-methane oxidation landfill cover system.

This study quantifies the field hydraulic performance of a dual-functionality landfill cover, combining microbial methane oxidation with water diversion using a capillary barrier. The investigated 500 m2 test field, constructed on a landfill in the Netherlands, consisted of a cover soil optimised for methane oxidation, underlain by a sandy capillary layer and a gravelly capillary block. Outflows from these layers were measured between 2009 and 2023. Average precipitation was 848 mm/a, evapotranspiration, diverted infiltration and breakthrough amounted to 504 (59.4 %), 282 (33.3 %) and 62 (7.3 %) mm/a, respectively. On average, the capillary barrier diverted 82 % of the inflow into the capillary layer. Breakthrough occurred mainly from October to March when evapotranspiration was low and the maximum water storage capacity of the cover soil was reached. During this period, inflow into the capillary barrier exceeded its diversion capacity, caused by the relatively high hydraulic conductivity of the cover soil due to its optimisation for gas transport. The diversion capacity declined drastically in the year after construction and increased again afterwards. This was attributed to suffusion of sand from the capillary layer into the capillary block and subsequent washout to greater depths or the influence of iron precipitates at the bottom of the capillary layer. The effect of a more finely grained methane oxidation layer on the hydraulic and methane oxidation performance should be investigated further. These measures could further improve the combined performance of the dual functionality landfill cover system under the given conditions of a temperate climate.

Atomically Dispersed Iron-Copper Dual-Metal Sites Synergistically Boost Carbonylation of Methane.

The direct liquid-phase oxidative carbonylation of methane, utilizing abundant natural gas, offers a mild and straightforward alternative. However, most catalysts proposed for this process suffer from low acetic acid yields due to few active sites and rapid C1 oxygenate generation, impeding their industrial feasibility. Herein, we report a highly efficient 0.1Cu/Fe-HZSM-5-TF (TF denotes template-free synthesis) catalyst featuring exclusively mononuclear Fe and Cu anchored in the ZSM-5 channels. Under optimized conditions, the catalyst achieved an unprecedented acetic acid yield of 40.5 mmol gcat -1 h-1 at 50 °C, tripling the previous records of 12.0 mmol gcat -1 h-1. Comprehensive characterization, isotope-labeled experiments and density functional theory (DFT) calculations reveal that the homogeneous mononuclear Fe sites are responsible for the activation and oxidation of methane, while the neighboring Cu sites play a key role in retarding the oxidation process, promoting C-C coupling for effective acetic acid synthesis. Furthermore, the methyl-group carbon in acetic acid originates solely from methane, while its carbonyl-group carbon is derived exclusively from CO, rather than the conversion of other C1 oxygenates. The proposed bimetallic catalyst design not only overcomes the limitations of current catalysts but also generalizes the oxidative carbonylation of other alkanes, demonstrating promising advancements in sustainable chemical synthesis.

Low-molecular-weight organic acids inhibit the methane-dependent arsenate reduction process in paddy soils.

Anaerobic methane oxidation (AOM) can drive soil arsenate reduction, a process known as methane-dependent arsenate reduction (M-AsR), which is a critical driver of arsenic (As) release in soil. Low molecular weight organic acids (LMWOAs), an important component of rice root exudates, have an unclear influence and mechanism on the M-AsR process. To narrow this knowledge gap, three typical LMWOAs-citric acid, oxalic acid, and acetic acid-were selected and added to As-contaminated paddy soils, followed by the injection of 13CH4 and incubation under anaerobic conditions. The results showed that LMWOAs inhibited the M-AsR process and reduced the As(III) concentration in soil porewater by 35.1-65.7 % after 14 days of incubation. Among the LMWOAs, acetic acid exhibited the strongest inhibition, followed by oxalic and citric acid. Moreover, LMWOAs significantly altered the concentrations of ferrous iron and dissolved organic carbon in the soil porewater, consequently impacting the release of As in the soil. The results of qPCR and sequencing analysis indicated that LMWOAs inhibited the M-AsR process by simultaneously suppressing microbes associated with ANME-2d and arrA. Our findings provide a theoretical basis for modulating the M-AsR process and enhance our understanding of the biogeochemical cycling of As in paddy soils under rhizosphere conditions.

Hydrogen-independent CO2 reduction dominates methanogenesis in five temperate lakes that differ in trophic states.

Emissions of microbially produced methane (CH4) from lake sediments are a major source of this potent greenhouse gas to the atmosphere. The rates of CH4 production and emission are believed to be influenced by electron acceptor distributions and organic carbon contents, which in turn are affected by anthropogenic inputs of nutrients leading to eutrophication. Here, we investigate how eutrophication influences the abundance and community structure of CH4 producing Archaea and methanogenesis pathways across time-resolved sedimentary records of five Swiss lakes with well-characterized trophic histories. Despite higher CH4 concentrations which suggest higher methanogenic activity in sediments of eutrophic lakes, abundances of methanogens were highest in oligotrophic lake sediments. Moreover, while the methanogenic community composition differed significantly at the lowest taxonomic levels (OTU), depending on whether sediment layers had been deposited under oligotrophic or eutrophic conditions, it showed no clear trend in relation to in situ distributions of electron acceptors. Remarkably, even though methanogenesis from CO2-reduction was the dominant pathway in all sediments based on carbon isotope fractionation values, taxonomic identities, and genomes of resident methanogens, CO2-reduction with hydrogen (H2) was thermodynamically unfavorable based on measured reactant and product concentrations. Instead, strong correlations between genomic abundances of CO2-reducing methanogens and anaerobic bacteria with potential for extracellular electron transfer suggest that methanogenic CO2-reduction in lake sediments is largely powered by direct electron transfer from syntrophic bacteria without involvement of H2 as an electron shuttle.

Investigating the Metal-TiO2 Influence for Highly Selective Photocatalytic Oxidation of Methane to Methanol.

Methane conversion to valuable chemicals is a highly challenging and desirable reaction. Photocatalysis is a clean pathway to drive this chemical reaction, avoiding the high temperature and pressure of the syngas process. Titanium dioxide, being the most used photocatalyst, presents challenges in controlling the oxidation process, which is believed to depend on the metal sites on its surface that function as heterojunctions. Herein, we supported different metals on TiO2 and evaluated their activity in methane photooxidation reactions. We showed that Ni-TiO2 is the best photocatalyst for selective methane conversion, producing impressively high amounts of methanol (1.600 µmol·g-1) using H2O2 as an oxidant, with minimal CO2 evolution. This performance is attributed to the high efficiency of nickel species to produce hydroxyl radicals and enhance H2O2 utilization as well as to induce carrier traps (Ti3+ and SETOVs sites) on TiO2, which are crucial for C-H activation. This study sheds light on the role of catalyst structure in the proper control of CH4 photoconversion.

Arcobacteraceae are ubiquitous mixotrophic bacteria playing important roles in carbon, nitrogen, and sulfur cycling in global oceans.

Mixotrophy is an important trophic strategy for bacterial survival in the ocean. However, the global relevance and identity of the major mixotrophic taxa remain largely elusive. Here, we combined phylogenetic, metagenomic, and metatranscriptomic analyses to characterize ubiquitous Arcobacteraceae based on our deep-sea in situ incubations and the global data. The phylogenomic tree of Arcobacteraceae is divided into three large clades, among which members of clades A and B are almost all from terrestrial environments, while those of clade C are widely distributed in various marine habitats in addition to some terrestrial origins. All clades harbor genes putatively involved in chitin degradation, sulfide oxidation, hydrogen oxidation, thiosulfate oxidation, denitrification, dissimilatory nitrate reduction to ammonium, microaerophilic respiration, and metal (iron/manganese) reduction. Additionally, in clade C, more unique pathways were retrieved, including thiosulfate disproportionation, ethanol fermentation, methane oxidation, fatty acid oxidation, cobalamin synthesis, and dissimilatory reductions of sulfate, perchlorate, and arsenate. Within this clade, two mixotrophic Candidatus genera represented by UBA6211 and CAIJNA01 harbor genes putatively involved in the reverse tricarboxylic acid pathway for carbon fixation. Moreover, the metatranscriptomic data in deep-sea in situ incubations indicated that the latter genus is a mixotroph that conducts carbon fixation by coupling sulfur oxidation and denitrification and metabolizing organic matter. Furthermore, global metatranscriptomic data confirmed the ubiquitous distribution and global relevance of Arcobacteraceae in the expression of those corresponding genes across all oceanic regions and depths. Overall, these results highlight the contribution of previously unrecognized Arcobacteraceae to carbon, nitrogen, and sulfur cycling in global oceans.IMPORTANCEMarine microorganisms exert a profound influence on global carbon cycling and ecological relationships. Mixotrophy, characterized by the simultaneous utilization of both autotrophic and heterotrophic nutrition, has a significant impact on the global carbon cycling. This report characterizes a group of uncultivated bacteria Arcobacteraceae that thrived on the "hot time" of bulky particulate organic matter and exhibited mixotrophic strategy during the in situ organic mineralization. Compared with clades A and B, more unique metabolic pathways were retrieved in clade C, including the reverse tricarboxylic acid pathway for carbon fixation, thiosulfate disproportionation, methane oxidation, and fatty acid oxidation. Global metatranscriptomic data from the Tara Oceans expeditions confirmed the ubiquitous distribution and extensive transcriptional activity of Arcobacteraceae with the expression of genes putatively involved in carbon fixation, methane oxidation, multiple sulfur compound oxidation, and denitrification across all oceanic regions and depths.

Precipitation and evaporation affecting landfill gas migration into passive methane oxidation biosystems: Models development and verification.

Passive methane oxidation biosystems (PMOBs) are developed as an innovative and cost-effective solution to reduce methane (CH4) emissions from municipal solid waste landfills. A PMOB consists of a methane oxidation layer (MOL) and an underlying gas distribution layer (GDL). The length of unrestricted gas migration (LUGM) has been recently proposed as the design criterion for PMOBs where the LUGM is calculated as the horizontal length along the MOL-GDL interface with the volumetric gas content (θa) exceeding the threshold volumetric gas content (θa,occ). This paper examined water and gas migration within three PMOBs with different MOL-GDL interfaces subject to precipitation and evaporation using verified numerical models. The results show that the use of a single-phase flow model underestimates the LUGM values of the PMOB for heavy precipitation events, and a two-phase flow model should be used to calculate both the LUGM and the total gas mass flow rate into the MOL when designing PMOBs. Both zig-zag and trapezoidal MOL-GDL interfaces can redistribute the gas mass flow rate at the MOL-GDL interface, while the trapezoidal MOL-GDL interface slightly outperforms the zig-zag MOL-GDL interface for enhancing the total gas mass flow rate into the MOL when comparing with the planar MOL-GDL interface. The zig-zag and trapezoidal MOL-GDL interfaces allow gas migration in the upper part of each PMOB segment even when the lower part of each PMOB segment was filled with water, and thus have a potential to minimize hotspot formation.