Aerobic Methane Oxidation Research Articles

A carbonate corrosion experiment at a marine methane seep: The role of aerobic methanotrophic bacteria.

Methane seeps are typified by the formation of authigenic carbonates, many of which exhibit corrosion surfaces and secondary porosity believed to be caused by microbial carbonate dissolution. Aerobic methane oxidation and sulfur oxidation are two processes capable of inducing carbonate corrosion at methane seeps. Although the potential of aerobic methanotrophy to dissolve carbonate was confirmed in laboratory experiments, this process has not been studied in the environment to date. Here, we report on a carbonate corrosion experiment carried out in the REGAB Pockmark, Gabon-Congo-Angola passive margin, in which marble cubes were deployed for 2.5 years at two sites (CAB-B and CAB-C) with apparent active methane seepage and one site (CAB-D) without methane seepage. Marble cubes exposed to active seepage (experiment CAB-C) were found to be affected by a new type of microbioerosion. Based on 16S rRNA gene analysis, the biofilms adhering to the bioeroded marble mostly consisted of aerobic methanotrophic bacteria, predominantly belonging to the uncultured Hyd24-01 clade. The presence of abundant 13 C-depleted lipid biomarkers including fatty acids (n-C16:1ω8c , n-C18:1ω8c , n-C16:1ω5t ), various 4-mono- and 4,4-dimethyl sterols, and diplopterol agrees with the dominance of aerobic methanotrophs in the CAB-C biofilms. Among the lipids of aerobic methanotrophs, the uncommon 4α-methylcholest-8(14)-en-3β,25-diol is interpreted to be a specific biomarker for the Hyd24-01 clade. The combination of textural, genetic, and organic geochemical evidence suggests that aerobic methanotrophs are the main drivers of carbonate dissolution observed in the CAB-C experiment at the REGAB pockmark.

Microbial survival mechanisms within serpentinizing Mariana forearc sediments.

Marine deep subsurface sediment is often a microbial environment under energy-limited conditions. However, microbial life has been found to persist and even thrive in deep subsurface environments. The Mariana forearc represents an ideal location for determining how microbial life can withstand extreme conditions including pH 10-12.5 and depleted nutrients. The International Ocean Discovery Program Expedition 366 to the Mariana Convergent Margin sampled three serpentinizing seamounts located along the Mariana forearc chain with elevated concentrations of methane, hydrogen, and sulfide. Across all three seamount summits, the most abundant transcripts were for cellular maintenance such as cell wall and membrane repair, and the most abundant metabolic pathways were the Entner-Doudoroff pathway and tricarboxylic acid cycle. At flank samples, sulfur cycling involving taurine assimilation dominated the metatranscriptomes. The in situ activity of these pathways was supported by the detection of their metabolic intermediates. All samples had transcripts from all three domains of Bacteria, Archaea, and Eukarya, dominated by Burkholderiales, Deinococcales, and Pseudomonales, as well as the fungal group Opisthokonta. All samples contained transcripts for aerobic methane oxidation (pmoABC) and denitrification (nirKS). The Mariana forearc microbial communities show activity not only consistent with basic survival mechanisms, but also coupled metabolic reactions.

The emission of low pH water from Gulf of Mexico seeps as revealed by δ13C–CO2 and methane oxidation data

During investigations of aerobic methane oxidation, this study found that seafloor seeps emit low pH water alongside methane. This discovery was revealed through isotopic measurement and model experiments.

Numerical analysis of moisture and gas transport in earthen final covers considering effects of vapor and temperature gradient

Biochemical decomposition of high kitchen wastes in landfills in China results in (i) a high content of vapor in landfill gas (LFG) and (ii) a noticeable temperature gradient across the earthen final cover (EFC). Yet, it is unclear how vapor and temperature gradients affect moisture and gas transport through EFC and microbial aerobic methane oxidation (MAMO). A theoretical model of moisture-gas-heat reactive transport considering MAMO and effects of vapor flow and temperature gradients was developed, and a series of parametric studies were included. The model was verified by published test results. The parametric simulation results show that vapor from landfill wastes can replenish water to EFCs in dry seasons, which results in (i) the relief of water shortage of vegetation and MAMO and (ii) LFG emission reduction. Effects of vapor inflow become more significant under larger temperature gradient. In cold seasons, temperature gradients can promote MAMO to reduce methane emissions, and enhance evaporation to reduce percolation. When evaporation rate at the surface exceeds 30 times vapor influx, vapor inflow has negligible effects on moisture and gas transport in EFCs. Neglecting effects of vapor and temperature gradient can lead to misjudgments on anti-seepage performance and methane emission reduction performance of EFCs.

Exploration of Fe speciation preference for aerobic methane oxidation by using isotopic Fe-modified zeolites

Methane-oxidizing bacteria (MOB) dominate the natural consumption of fugitive methane (CH4), which is largely produced by methanogens in aerobic-anaerobic habitats. Although the influence of iron (Fe) on MOB activities has been examined, the underlying mechanism in terms of the preference remains to be clarified, the key to which may be the extracellular uptake of Fe during CH4 oxidation. In this study, isotopic ferric chloride was used to treat stable raw zeolites (Fe-Z) through a pyrolytic procedure (Fe-Z600). All samples were allowed to develop for 52 d, and the CH4 oxidation rate and contents of Fe and extracellular polymers (EPS) in different MOB periods were determined. The cumulative oxidation mass of CH4 in Fe-Z600 was two times that in Fe-Z, and the abundance of Methylocystis in Fe-Z600 was 21% higher. More uniformly dispersed α-Fe2O3 nanoparticles were formed during the pyrolysis of Fe-Z600, which accelerated the extracellular migration and stimulated MOB growth. In addition, Fe-Z600 presented the strongest extracellular polysaccharides (ECPs) inhibition; the total amount of ECPs was about 53.9% lower than that of the Raw group. Simultaneously, Fe was more likely to be stored in loosely bound EPS (LB-EPS), with a maximum cumulative amount of 38% during the stable period of CH4 oxidation in Fe-Z600, decreasing LB-EPS and tightly bound EPS by 47.4% and 75.4%, respectively. The presented findings can provide guidance for alleviating EPS blockage in long-term activities of MOB to ensure their efficient and durable CH4 oxidation.

Aerobic oxidation of methane significantly reduces global diffusive methane emissions from shallow marine waters

Methane is supersaturated in surface seawater and shallow coastal waters dominate global ocean methane emissions to the atmosphere. Aerobic methane oxidation (MOx) can reduce atmospheric evasion, but the magnitude and control of MOx remain poorly understood. Here we investigate methane sources and fates in the East China Sea and map global MOx rates in shallow waters by training machine-learning models. We show methane is produced during methylphosphonate decomposition under phosphate-limiting conditions and sedimentary release is also source of methane. High MOx rates observed in these productive coastal waters are correlated with methanotrophic activity and biomass. By merging the measured MOx rates with methane concentrations and other variables from a global database, we predict MOx rates and estimate that half of methane, amounting to 1.8 ± 2.7 Tg, is consumed annually in near-shore waters (<50 m), suggesting that aerobic methanotrophy is an important sink that significantly constrains global methane emissions.

Differential patterns and assembly processes of bacterial communities from distinct microhabitats in a subtropical estuary

Estuarine ecosystems interconnect freshwater and marine environments, and comprise multiple highly dynamic and complex microhabitats. The resident microbiota in estuary is influenced by contrasting microenvironmental heterogeneity. However, the bacterial patterns and assembly processes in different microhabitats of estuarine ecosystem are not well studied. Here, we investigated the bacterial diversity, functions and community assembly mechanisms of mangrove soil, river sediment and overlying water in a subtropical estuary. Results showed that similar profiles of bacterial communities existed in the mangrove soil and river sediment and were dominated by Proteobacteria, Bacteroidetes and Acidobacteria. In terms of different microhabitats, the lowest alpha diversity of bacterial communities was found in overlying water and were dominated by Proteobacteria, Actinobacteria and Bacteroidetes. Meanwhile, the functional potential genes associated with carbon metabolisms were also substantially different in the three microhabitats. The relative abundance of genes connected to aerobic carbon respiration was significantly higher in overlying water than in the other two microhabitats. Bacterial communities in river sediments were enriched for genes associated with aerobic methane oxidation. The strong environmental heterogeneity of the three nearby microhabitats shaped the taxonomic and functional composition of the bacterial communities in estuarine ecosystem. Moreover, the plant rhizosphere effect increased the proportion of the dispersal limitation processes in mangrove soils compared to that in river sediments, while the overlying water was fluid and had less environmental selection processes compared to that in mangrove soil and river sediment. The bacterial communities in river sediment construct a more clustered network, while the overlying water network showed the highest complexity. Our findings reveal the differences of bacterial patterns and community assembly mechanisms in distinct microhabitats of estuarine ecosystems, and provide important insights for a comprehensive understanding of the mechanisms to maintain estuarine wetland conservation under environmental changes.

Biofilm stratification in counter-diffused membrane biofilm bioreactors (MBfRs) for aerobic methane oxidation coupled to aerobic/anoxic denitrification: Effect of oxygen pressure

Aerobic methane oxidation coupled with denitrification (AME-D) executed in membrane biofilm bioreactors (MBfRs) provides a high promise for simultaneously mitigating methane (CH4) emissions and removing nitrate in wastewater. However, systematically experimental investigation on how oxygen partial pressure affects the development and characteristics of counter-diffusional biofilm, as well as its spatial stratification profiles, and the cooperative interaction of the biofilm microbes, is still absent. In this study, we combined Optical Coherence Tomography (OCT) with Confocal Laser Scanning Microscopy (CLSM) to in-situ characterize the development of counter-diffusion biofilm in the MBfR for the first time. It was revealed that oxygen partial pressure onto the MBfR was capable of manipulating biofilm thickness and spatial stratification, and then managing the distribution of functional microbes. With the optimized oxygen partial pressure of 5.5 psig (25% oxygen content), the manipulated counter-diffusional biofilm in the AME-D process obtained the highest denitrification efficiency, due mainly to that this biofilm had the proper dynamic balance between the aerobic-layer and anoxic-layer where suitable O2 gradient and sufficient aerobic methanotrophs were achieved in aerobic-layer to favor methane oxidation, and complete O2 depletion and accessible organic sources were kept to avoid constraining denitrification activity in anoxic-layer. By using metagenome analysis and Fluorescence in situ hybridization (FISH) staining, the spatial distribution of the functional microbes within counter-diffused biofilm was successfully evidenced, and Rhodocyclaceae, one typical aerobic denitrifier, was found to survive and gradually enriched in the aerobic layer and played a key role in denitrification aerobically. This in-situ biofilm visualization and characterization evidenced directly for the first time the cooperative path of denitrification for AME-D in the counter-diffused biofilm, which involved aerobic methanotrophs, heterotrophic aerobic denitrifiers, and heterotrophic anoxic denitrifiers.

Variability and controls of stable carbon isotopic fractionation during aerobic methane oxidation in temperate lakes

The aerobic oxidation of methane (CH4) by methanotrophic bacteria (MOB) is the major sink of this highly potent greenhouse gas in freshwater environments. Yet, CH4 oxidation is one of the largest uncertain components in predicting the current and future CH4 emissions from these systems. While stable carbon isotopic mass balance is a powerful approach to estimate the extent of CH4 oxidation in situ, its applicability is constrained by the need of a reliable isotopic fractionation factor (αox), which depicts the slower reaction of the heavier stable isotope (13C) during CH4 oxidation. Here we explored the natural variability and the controls of αox across the water column of six temperate lakes using experimental incubation of unamended water samples at different temperatures. We found a large variability of αox (1.004–1.038) with a systematic increase from the surface to the deep layers of lake water columns. Moreover, αox was strongly positively coupled to the abundance of MOB in the γ-proteobacteria class (γ-MOB), which in turn correlated to the concentrations of oxygen and CH4, and to the rates of CH4 oxidation. To enable the applicability in future isotopic mass balance studies, we further developed a general model to predict αox using routinely measured limnological variables. By applying this model to δ13C-CH4 profiles obtained from the study lakes, we show that using a constant αox value in isotopic mass balances can largely misrepresent and undermine patterns of the extent of CH4 oxidation in lakes. Our αox model thus contributes towards more reliable estimations of stable carbon isotope-based quantification of CH4 oxidation and may help to elucidate large scale patterns and drivers of the oxidation-driven mitigation of CH4 emission from lakes.

Response of benthic foraminifera to environmental successions of cold seeps from Vestnesa Ridge, Svalbard: Implications for interpretations of paleo-seepage environments

This paper presents the results of a study on the response of living benthic foraminifera to progressing environmental successions in a cold-seep ecosystem. Sediment samples were collected from Vestnesa Ridge (79°N, Fram Strait) at ~1200 m water depth. The distribution of live (Rose Bengal-stained) foraminifera were analyzed in the upper sediment layers in relation to pore water biogeochemical data together with the distribution of sulfur-bacterial mats and Siboglinidae tubeworms. At methane cold seeps, the process of environmental succession is strongly connected to the duration and strength of methane seepage and the intensity of methane-related biological processes, e.g, aerobic and anaerobic oxidation of methane (MOx and AOM, respectively). The results show that the distribution patterns of benthic foraminifera change according to the progressing environmental succession. The benthic foraminifera seemed to thrive in sediments with a moderate activity of seepage, dominated by MOx, i.e, at an early stage of seepage or when seepage decreases at a late stage of the succession. Species composition of the foraminiferal fauna under these conditions was similar to the control sites (outside of pockmarks with no seepage); the dominant species being Melonis barleeanus and Cassidulina neoteretis. In sediments with strong seepage and high AOM activity, the hostile environmental conditions due to the presence of toxic sulfide caused a reduction in the foraminiferal population, and samples were almost barren of foraminifera. In environments of moderate methane seepage, the presence of chemosynthetic Siboglinidae tube worms potentially support communities of the epibenthic species Cibicidoides wuellerstorfi. Despite the very different environmental conditions, the foraminiferal assemblages were very similar (or nearly absent). Therefore, the foraminiferal faunas cannot be used as exclusive indicators of past strength of methane seepage in palaeoceanographic interpretations.

Platinum-Catalysed Selective Aerobic Oxidation of Methane to Formaldehyde in the Presence of Liquid Water.

The aerobic, selective oxidation of methane to C1‐oxygenates remains a challenge, due to the more facile, consecutive oxidation of formed products to CO2. Here, we report on the aerobic selective oxidation of methane under continuous flow conditions, over platinum‐based catalysts yielding formaldehyde with a high selectivity (reaching 90 % for Pt/TiO2 and 65 % over Pt/Al2O3) upon co‐feeding water. The presence of liquid water under reaction conditions increases the activity strongly attaining a methane conversion of 1–3 % over Pt/TiO2. Density‐functional theory (DFT) calculations show that the preferential formation of formaldehyde is linked to the stability of the di‐σ‐hydroxy‐methoxy species on platinum, the preferred carbon‐containing species on Pt(111) at a high chemical potential of water. Our findings provide novel insights into the reaction pathway for the Pt‐catalysed, aerobic selective oxidation of CH4.

Platinum‐Catalysed Selective Aerobic Oxidation of Methane to Formaldehyde in the Presence of Liquid Water

AbstractThe aerobic, selective oxidation of methane to C1‐oxygenates remains a challenge, due to the more facile, consecutive oxidation of formed products to CO2. Here, we report on the aerobic selective oxidation of methane under continuous flow conditions, over platinum‐based catalysts yielding formaldehyde with a high selectivity (reaching 90 % for Pt/TiO2 and 65 % over Pt/Al2O3) upon co‐feeding water. The presence of liquid water under reaction conditions increases the activity strongly attaining a methane conversion of 1–3 % over Pt/TiO2. Density‐functional theory (DFT) calculations show that the preferential formation of formaldehyde is linked to the stability of the di‐σ‐hydroxy‐methoxy species on platinum, the preferred carbon‐containing species on Pt(111) at a high chemical potential of water. Our findings provide novel insights into the reaction pathway for the Pt‐catalysed, aerobic selective oxidation of CH4.

Elevating Photooxidation of Methane to Formaldehyde via TiO2 Crystal Phase Engineering

Photocatalytic conversion of methane to value-added products under mild conditions, which represents a long sought-after goal for industrial sustainable production, remains extremely challenging to afford high production and selectivity using cheap catalysts. Herein, we present the crystal phase engineering of commercially available anatase TiO2 via simple thermal annealing to optimize the structure-property correlation. A biphase catalyst with anatase (90%) and rutile (10%) TiO2 with the optimal phase interface concentration exhibits exceptional performance in the oxidation of methane to formaldehyde under the reaction conditions of water solvent, oxygen atmosphere, and full-spectrum light irradiation. An unprecedented production of 24.27 mmol gcat-1 with an excellent selectivity of 97.4% toward formaldehyde is acquired at room temperature after a 3 h reaction. Both experimental results and theoretical calculations disclose that the crystal phase engineering of TiO2 lengthens the lifetime of photogenerated carriers and favors the formation of intermediate methanol species, thus maximizing the efficiency and selectivity in the aerobic oxidation of methane to formaldehyde. More importantly, the feasibility of the scale-up production of formaldehyde is demonstrated by inventing a "pause-flow" reactor. This work opens the avenue toward industrial methane transformation in a sustainable and economical way.

The Effects of Engineered Aeration on Atmospheric Methane Flux From a Chesapeake Bay Tidal Tributary

Engineered aeration is one solution for increasing oxygen concentrations in highly eutrophic estuaries that undergo seasonal hypoxia. Although there are various designs for engineered aeration, all approaches involve either destratification of the water column or direct injection of oxygen or air through fine bubble diffusion. To date, the effect of either approach on estuarine methane dynamics remains unknown. Here we tested the hypotheses that 1) bubble aeration will strip the water of methane and enhance the air-water methane flux to the atmosphere and 2) the addition of oxygen to the water column will enhance aerobic methane oxidation in the water column and potentially offset the air-water methane flux. These hypotheses were tested in Rock Creek, Maryland, a shallow-water sub-estuary to the Chesapeake Bay, using controlled, ecosystem-scale deoxygenation experiments where the water column and sediments were sampled in mid-summer, when aerators were ON, and then 1, 3, 7, and 13 days after the aerators were turned OFF. Experiments were performed under two system designs, large bubble and fine bubble approaches, using the same observational approach that combined discrete water sampling, long term water samplers (OsmoSamplers) and sediment porewater profiles. Regardless of aeration status, methane concentrations reached as high as 1,500 nmol L−1 in the water column during the experiments and remained near 1,000 nmol L−1 through the summer and into the fall. Since these concentrations are above atmospheric equilibrium of 3 nmol L−1, these data establish the sub-estuary as a source of methane to the atmosphere, with a maximum atmospheric flux as high as 1,500 µmol m−2 d−1, which is comparable to fluxes estimated for other estuaries. Air-water methane fluxes were higher when the aerators were ON, over short time frames, supporting the hypothesis that aeration enhanced the atmospheric methane flux. The fine-bubble approach showed lower air-water methane fluxes compared to the larger bubble, destratification system. We found that the primary source of the methane was the sediments, however, in situ methane production or an upstream methane source could not be ruled out. Overall, our measurements of methane concentrations were consistently high in all times and locations, supporting consistent methane flux to the atmosphere.

A novel Methylomirabilota methanotroph potentially couples methane oxidation to iodate reduction.

Methane oxidizing microbes play a key role in reducing the emission of this potent greenhouse gas to the atmosphere. The known versatility of the recently discovered anaerobic Methylomirabilota methanotrophs is limited. Here, we report a novel uncultured Methylomirabilis species, Candidatus Methylomirabilis iodofontis, with the genetic potential of iodate respiration from biofilm in iodine-rich cavern spring water. Star-like cells resembling Methylomirabilis oxyfera were directly observed from the biofilm and a high-quality metagenome-assembled genome (MAG) of Ca. M. iodofontis was assembled. In addition to oxygenic denitrification and aerobic methane oxidation pathways, the M. iodofontis MAG also indicated its iodate-reducing potential, a capability that would enable the bacterium to use iodate other than nitrite as an electron acceptor, a hitherto unrecognized metabolic potential of Methylomirabilota methanotrophs. The results advance the current understanding of the ecophysiology of anaerobic Methylomirabilota methanotrophs and may suggest an additional methane sink, especially in iodate-rich ecosystems.

Coupled Aerobic Methane Oxidation and Arsenate Reduction Contributes to Soil-Arsenic Mobilization in Agricultural Fields.

Microbial oxidation of organic compounds can promote arsenic release by reducing soil-associated arsenate to the more mobile form arsenite. While anaerobic oxidation of methane has been demonstrated to reduce arsenate, it remains elusive whether and to what extent aerobic methane oxidation (aeMO) can contribute to reductive arsenic mobilization. To fill this knowledge gap, we performed incubations of both microbial laboratory cultures and soil samples from arsenic-contaminated agricultural fields in China. Incubations with laboratory cultures showed that aeMO could couple to arsenate reduction, wherein the former bioprocess was carried out by aerobic methanotrophs and the latter by a non-methanotrophic bacterium belonging to a novel and uncultivated representative of Burkholderiaceae. Metagenomic analyses combined with metabolite measurements suggested that formate served as the interspecies electron carrier linking aeMO to arsenate reduction. Such coupled bioprocesses also take place in the real world, supported by a similar stoichiometry and gene activity in the incubations with natural paddy soils, and contribute up to 76.2% of soil-arsenic mobilization into pore waters in the top layer of the soils where oxygen was present. Overall, this study reveals a previously overlooked yet significant contribution of aeMO to reductive arsenic mobilization.

Formula omitted] and [formula omitted] signatures of methane aerobically oxidized by Methylosinus trichosporium with implications for deciphering the provenance of methane gases

Aerobic oxidation of methane (MOx) is an important biologically mediated process that consumes methane in a wide range of environments. Here we report results of culture experiments with the aerobic methane-oxidizing bacterium Methylosinus trichosporium (OB3b) that are used to characterize the mass-18 isotopologue (Δ13CH3D and Δ12CH2D2) signatures of MOx in residual methane gases. MOx activity was confirmed by simultaneous decrease of methane and oxygen in the bulk gas headspace. Bulk carbon (13C/12C) and hydrogen (D/H) isotope ratios of the methane gas increased while both Δ13CH3D and Δ12CH2D2 decreased as the oxidation proceeded. The corresponding fractionation factors (α) calculated from our experimental results are 0.98485 ± 0.00006 for 13C/12C, 0.7265 ± 0.0010 for D/H, 0.7141 ± 0.0011 for 13CH3D/12CH4, and 0.4757 ± 0.0023 for 12CH2D2/12CH4. Deviations of the mass-18 fractionation factors from the Rule of the Geometric Mean (RGM) expressed as γ values are 0.9981 ± 0.0017 for 13CH3D/12CH4 and 0.9013 ± 0.0045 for 12CH2D2/12CH4. Our α and γ values suggest that while MOx fractionates 13CH3D within error of the RGM, the Δ13CH3D and Δ12CH2D2 trajectories are very sensitive to even small deviations in 13CH3D/12CH4 from the RGM. Fractionation of 12CH2D2 deviates considerably from RGM, and this causes dramatic and robust effects on the trajectories of residual methane in Δ13CH3D vs. Δ12CH2D2 space. Our models suggest that Δ13CH3D and Δ12CH2D2 could potentially mimic microbial methanogenesis signatures in an environment that exhibits a strong Rayleigh Distillation process with little to no replenishment of methane during oxidation. However, in closed or open systems where oxidation is attended by simultaneous methane production, we find that modest increases in Δ13CH3D and dramatic increases in Δ12CH2D2 are to be expected, thus resulting in isotopologue signatures distinct from microbial methanogenesis. The overall trend in these conditions suggest that methane altered by MOx is distinguishable from other methane sources in Δ13CH3D and Δ12CH2D2 space.

Bacteriohopanepolyols across the Black Sea redoxcline trace diverse bacterial metabolisms

Redox gradients in oceanic oxygen minimum zones are hotspots of diverse bacterial populations and metabolisms. Here, we test whether bacteriohopanepolyols (BHPs), a suite of membrane-regulating pentacyclic triterpenoid lipids, are suitable tracers of major bacterial metabolisms and whether their structural diversity (BHP lipidomics) allows tracing the bacterial ecology across the Black Sea chemocline. We analyzed suspended particulate matter (SPM) sampled along depth-profiles across the redox/chemocline at two sites in the eastern and western gyres and underlying core-top sediments at the western gyre site. Our results show that BHPs abundances reflect the stratification of the Black Sea and capture ecological niches across the chemocline, being highest in the lower suboxic zone and in upper to deep sulfidic waters. BHP-inferred bacterial metabolisms in the lower suboxic zone are dominated by anammox and aerobic methane oxidizers (primarily by Type I/gammaproteobacteria). Bacterial biomass production in the upper to deep sulfidic zone is mirrored by a range of BHPs that are normally associated with aerobic metabolisms, most likely explained by either survival in oxygenated micro-niches or production by anaerobic bacteria (which could possibly include sulfate reducers and nitrite-dependent methane oxidizers). Most surprisingly, this ecological niche harbors seemingly unknown anaerobic bacteria which produce abundant C-2 and C-3 methylated BHPs. Core-top sediments reflect the BHP structural diversity found in SPM, but with notable compositional differences. Most strikingly, the export dynamics seem to result in near-absence of C-2 methylated BHPs in surface sediments. Sedimentary BHP distributions therefore underestimate the importance of C-2 methylated BHPs in the water column, which has implications for the geological record.

Copper mobilisation from Cu sulphide minerals by methanobactin: Effect of pH, oxygen and natural organic matter.

Aerobic methane oxidation (MOx) depends critically on the availability of copper (Cu) as a crucial component of the metal centre of particulate methane monooxygenase, one of the main enzymes involved in MOx. Some methanotrophs have developed Cu acquisition strategies, in which they exude Cu‐binding ligands termed chalkophores under conditions of low Cu availability. A well‐characterised chalkophore is methanobactin (mb), exuded by the microaerophilic methanotroph Methylosinus trichosporium OB3b. Aerobic methanotrophs generally reside close to environmental oxic–anoxic interfaces, where the formation of Cu sulphide phases can aggravate the limitation of bioavailable Cu due to their low solubility. The reactivity of chalkophores towards such Cu sulphide mineral phases has not yet been investigated. In this study, a combination of dissolution experiments and equilibrium modelling was used to examine the dissolution and solubility of bulk and nanoparticulate Cu sulphide minerals in the presence of mb as influenced by pH, oxygen and natural organic matter. In general, we show that mb is effective at increasing the dissolved Cu concentrations in the presence of a variety of Cu sulphide phases that may potentially limit Cu bioavailability. More Cu was mobilised per mole of mb from Cu sulphide nanoparticles compared with well‐crystalline bulk covellite (CuS). In general, the efficacy of mb at mobilising Cu from Cu sulphides is pH‐dependent. At lower pH, e.g. pH 5, mb was ineffective at solubilizing Cu. The presence of mb increased dissolved Cu concentrations between pH 7 and 8.5, where the solubility of all Cu sulphides is generally low, both in the presence and absence of oxygen. These results suggest that chalkophore‐promoted Cu mobilisation from sulphide phases is an effective extracellular mechanism for increasing dissolved Cu concentrations at oxic–anoxic interfaces, particularly in the neutral to slightly alkaline pH range. This suggests that aerobic methanotrophs may be able to fulfil their Cu requirements via the exudation of mb in natural environments where the bioavailability of Cu is constrained by very stable Cu sulphide phases.

Photocatalytic Methane Conversion: Insight into the Mechanism of C(sp 3 )–H Bond Activation

Photocatalytic Methane Conversion: Insight into the Mechanism of C(sp ³ )–H Bond Activation