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.

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.

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 ∼ 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.

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.

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.

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.

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.

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.

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.

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.