Anaerobic Oxidation Of Methane Rates Research Articles

Methyl-compounds driven benthic carbon cycling in the sulfate-reducing sediments of South China Sea.

Methane is a potent greenhouse gas; methane production and consumption within seafloor sediments has generated intense interest. Anaerobic oxidation of methane (AOM) and methanogenesis (MOG) primarily occur at the depth of the sulfate-methane transition zone or underlying sediment respectively. Methanogenesis can also occur in the sulfate-reducing sediments through the utilization of non-competitive methylated compounds; however, the occurrence and importance of this process are not fully understood. Here, we combined a variety of data, including geochemical measurements, rate measurements and molecular analyses to demonstrate the presence of a cryptic methane cycle in sulfate-reducing sediments from the continental shelf of the northern South China Sea. The abundance of methanogenic substrates as well as the high MOG rates from methylated compounds indicated that methylotrophic methanogenesis was the dominant methanogenic pathway; this conclusion was further supported by the presence of the methylotrophic genus Methanococcoides. High potential rates of AOM were observed in the sediments, indicating that methane produced in situ could be oxidized simultaneously by AOM, presumably by ANME-2a/b as indicated by 16S rRNA gene analysis. A significant correlation between the relative abundance of methanogens and methanotrophs was observed over sediment depth, indicating that methylotrophic methanogenesis could potentially fuel AOM in this environment. In addition, higher potential rates of AOM than sulfate reduction rates at in situ methane conditions were observed, making alternative electron acceptors important to support AOM in sulfate-reducing sediment. AOM rates were stimulated by the addition of Fe/Mn oxides, suggesting AOM could be partially coupled to metal oxide reduction. These results suggest that methyl-compounds driven methane production drives a cryptic methane cycling and fuels AOM coupled to the reduction of sulfate and other electron acceptors.

Influence of electron acceptor availability and microbial community structure on sedimentary methane oxidation in a boreal estuary

Methane is produced microbially in vast quantities in sediments throughout the world’s oceans. However, anaerobic oxidation of methane (AOM) provides a near-quantitative sink for the produced methane and is primarily responsible for preventing methane emissions from the oceans to the atmosphere. AOM is a complex microbial process that involves several different microbial groups and metabolic pathways. The role of different electron acceptors in AOM has been studied for decades, yet large uncertainties remain, especially in terms of understanding the processes in natural settings. This study reports whole-core incubation methane oxidation rates along an estuarine gradient ranging from near fresh water to brackish conditions, and investigates the potential role of different electron acceptors in AOM. Microbial community structure involved in different methane processes is also studied in the same estuarine system using high throughput sequencing tools. Methane oxidation in the sediments was active in three distinct depth layers throughout the studied transect, with total oxidation rates increasing seawards. We find extensive evidence of non-sulphate AOM throughout the transect. The highest absolute AOM rates were observed below the sulphate-methane transition zone (SMTZ), strongly implicating the role of alternative electron acceptors (most likely iron and manganese oxides). However, oxidation rates were ultimately limited by methane availability. ANME-2a/b were the most abundant microbial phyla associated with AOM throughout the study sites, followed by ANME-2d in much lower abundances. Similarly to oxidation rates, highest abundances of microbial groups commonly associated with AOM were found well below the SMTZ, further reinforcing the importance of non-sulphate AOM in this system.

A Quantitative Assessment of Methane-Derived Carbon Cycling at the Cold Seeps in the Northwestern South China Sea

Widespread cold seeps along continental margins are significant sources of dissolved carbon to the ocean water. However, little is known about the methane turnovers and possible impact of seepage on the bottom seawater at the cold seeps in the South China Sea (SCS). We present seafloor observation and porewater data of six push cores, one piston core and three boreholes as well as fifteen bottom-water samples collected from four cold seep areas in the northwestern SCS. The depths of the sulfate–methane transition zone (SMTZ) are generally shallow, ranging from ~7 to <0.5 mbsf (meters below seafloor). Reaction-transport modelling results show that methane dynamics were highly variable due to the transport and dissolution of ascending gas. Dissolved methane is predominantly consumed by anaerobic oxidation of methane (AOM) at the SMTZ and trapped by gas hydrate formation below it, with depth-integrated AOM rates ranging from 59.0 and 591 mmol m−2 yr−1. The δ13C and Δ14C values of bottom-water dissolved inorganic carbon (DIC) suggest discharge of 13C- and 14C-depleted fossil carbon to the bottom water at the cold seep areas. Based on a two-endmember estimate, cold seeps fluids likely contribute 16–26% of the bottom seawater DIC and may have an impact on the long-term deep-sea carbon cycle. Our results reveal the methane-related carbon inventories are highly heterogeneous in the cold seep systems, which are probably dependent on the distances of the sampling sites to the seepage center. To our knowledge, this is the first quantitative study on the contribution of cold seep fluids to the bottom-water carbon reservoir of the SCS, and might help to understand the dynamics and the environmental impact of hydrocarbon seep in the SCS.

Anaerobic Oxidation of Methane in Freshwater Sediments of Rzeszów Reservoir

The anaerobic oxidation of methane (AOM) is an important sink of methane that plays a significant role in global warming. However, evidence for the AOM in freshwater habitats is rare, especially in dam and weir (small-scale dam) reservoirs. Here, the AOM process was examined in freshwater sediments of a small-scale dam reservoir located in Rzeszów, SE Poland. The AOM rate was determined in the main experiment with the addition of the 13CH4 isotope marker (He+13CH4). Sediments were collected three times: in spring (in May, 15 °C), in summer (in July, 20 °C) and in autumn (in September, 10 °C). Further analysis considers the impact on AOM rate of potential electron acceptors present in pore-water (NO2−, NO3−, SO42−, and Fe3+ ions). The work suggests that an AOM process does take place in the studied reservoir sediments, with this evidenced by the presence in the headspace of an increased 13CO2 concentration deemed to derive from 13CH4 oxidation. Rates of AOM noted were of 0.36–1.42 nmol·g−1·h−1, with the most intensive oxidation in each sediment layer occurring at 20 °C. While none of the potential electron acceptors considered individually were found to have had a statistically significant influence on the AOM rate, their significance to the dynamics of the AOM process was not precluded.

Anaerobic oxidation of methane in paddy soil: Role of electron acceptors and fertilization in mitigating CH4 fluxes

The anaerobic oxidation of methane (AOM) in marine ecosystems is ubiquitous and largely coupled to sulfate reduction. In contrast, the role of AOM in terrestrial environments and the dominant electron acceptors driving terrestrial AOM needs deeper understanding. Submerged rice paddies with intensive CH4 production have a high potential for AOM, which can be important for greenhouse gas mitigation strategies. Here, we used 13CH4 to quantify the AOM rates in paddy soils under organic (Pig manure, Biochar) and mineral (NPK) fertilization. Alternative-to-oxygen electron acceptors for CH4 oxidation, including Fe3+, NO3−, SO42−, and humic acids, were examined and their potential for CH4 mitigation from rice paddies was assessed by 13CH4 oxidation to 13CO2 under anoxic conditions.During 84 days of anaerobic incubation, the cumulative AOM (13CH4-derived CO2) reached 0.15–1.3 μg C g-1 dry soil depending on fertilization. NO3- was the most effective electron acceptor, yielding an AOM rate of 0.80 ng C g-1 dry soil h-1 under Pig manure. The role of Fe3+ in AOM remained unclear, whereas SO42- inhibited AOM but strongly stimulated the production of unlabeled CO2, indicating intensive sulfate-induced decomposition of organic matter. Humic acids were the second most effective electron acceptor for AOM, but increased methanogenesis by 5–6 times in all fertilization treatments. We demonstrated for the first time that organic electron acceptors (humic acids) are among the key AOM drivers and are crucial in paddy soils. The most pronounced AOM in paddy soils occurred under Pig manure, followed by Control and NPK, while AOM was the lowest under Biochar. We estimate that nitrate (nitrite)-dependent AOM in paddy fields globally consumes ~3.9 Tg C–CH4 yr-1, thereby offsetting the global CH4 emissions by ~10–20%. Thus, from a broader agroecological perspective, the organic and mineral fertilizers control an important CH4 sink under anaerobic conditions in submerged ecosystems. Appropriate adjustments of soil fertilization management strategies would therefore help to decrease the net CH4 flux to the atmosphere and hence the global warming.

Can anaerobic oxidation of methane prevent seafloor gas escape in a warming climate?

Abstract. Assessments of future climate-warming-induced seafloor methane (CH4) release rarely include anaerobic oxidation of methane (AOM) within the sediments. Considering that more than 90 % of the CH4 produced in ocean sediments today is consumed by AOM, this may result in substantial overestimations of future seafloor CH4 release. Here, we integrate a fully coupled AOM module with a numerical hydrate model to investigate under what conditions rapid release of CH4 can bypass AOM and result in significant fluxes to the ocean and atmosphere. We run a number of different model simulations for different permeabilities and maximum AOM rates. In all simulations, a future climate warming scenario is simulated by imposing a linear seafloor temperature increase of 3 ∘C over the first 100 years. The results presented in this study should be seen as a first step towards understanding AOM dynamics in relation to climate change and hydrate dissociation. Although the model is somewhat poorly constrained, our results indicate that vertical CH4 migration through hydraulic fractures can result in low AOM efficiencies. Fracture flow is the predicted mode of methane transport under warming-induced dissociation of hydrates on upper continental slopes. Therefore, in a future climate warming scenario, AOM might not significantly reduce methane release from marine sediments.

Methane Source and Turnover in the Shallow Sediments to the West of Haima Cold Seeps on the Northwestern Slope of the South China Sea

The Haima cold seeps are active cold seep areas that were recently discovered on the northwestern slope of the South China Sea (SCS). Three piston cores (CL30, CL44, and CL47) were collected within an area characterized by bottom simulating reflectors to the west of Haima cold seeps. Porewater profiles of the three cores exhibit typical kink-type feature, which is attributed to elevated methane flux (CL30) and bubble irrigation (CL44 and CL47). By simulating the porewater profiles of SO42-, CH4, PO43-, Ca2+, Mg2+, and dissolved inorganic carbon (DIC) in CL44 and CL47 using a steady-state reaction-transport model, we estimated that the dissolved SO42- was predominantly consumed by anaerobic oxidation of methane (AOM) at rates of 74.3 mmol m−2 yr−1 in CL44 and 85.0 mmol m−2 yr−1 in CL47. The relatively high AOM rates were sustained by free gas dissolution rather than local methanogenesis. Based on the diffusive Ba2+ fluxes and the excess barium contents in the sediments slightly above the current SMTZ, we estimated that methane fluxes at core CL44 and CL47 have persisted for ca. 3 kyr and 0.8-1.6 kyr, respectively. The non-steady-state modeling for CL30 predicted that a recent increase in upward dissolved methane flux was initiated ca. 85 yr ago. However, the required time for the formation of the barium front above the SMTZ at this core is much longer (ca. 2.2-4.2 kyr), which suggests that the depth of SMTZ possibly has fluctuated due to episodic changes in methane flux. Furthermore, using the model-derived fractions of different DIC sources and the δ13CDIC mass balance calculation, we estimated that the δ13C values of the external methane in cores CL30, CL44, and CL47 are -74.1‰, -75.4‰, and -66.7‰, respectively, indicating the microbial origin of methane. Our results suggest that methane seepage in the broader area surrounding the Haima cold seeps probably has persisted at least hundreds to thousands of years with changing methane fluxes.

Anaerobic methane oxidation coupled to sulfate reduction in a biotrickling filter: Reactor performance and microbial community analysis

The aim of this work was to evaluate the performance of a biotrickling filter (BTF) packed with polyurethane foam and pall rings for the enrichment of microorganisms mediating anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) by activity tests and microbial community analysis. A BTF was inoculated with microorganisms from a known AOM active deep sea sediment collected at a depth of 528 m below the sea level (Alpha Mound, Gulf of Cadiz). The microbial community analysis was performed by catalyzed reporter deposition - fluorescence in situ hybridization (CARD-FISH) and 16S rRNA sequence analysis. The AOM occurrence and rates in the BTF were assessed by performing batch activity assays using 13C-labelled methane (13CH4). After an estimated start-up time of ∼20 days, AOM rates of ∼0.3 mmol l−1 day−1 were observed in the BTF, values almost 20 times higher than previously reported in a polyurethane foam packed BTF. The microbial community consisted mainly of anaerobic methanotrophs (ANME-2, 22% of the total number of cells) and sulfate reducing bacteria (SRB, 47% of the total number of cells). This study showed that the BTF is a suitable reactor configuration for the enrichment of microbial communities involved in AOM coupled to SR at ambient pressure and temperature with a relatively short start-up time.

Evaluating radioisotope‐based approaches to measure anaerobic methane oxidation rates in lacustrine sediments

AbstractThe microbial anaerobic oxidation of methane (AOM) is the dominant sink for methane in anoxic sediments. AOM rate measurements are essential for assessing the efficacy of the benthic methane filter to mitigate the evasion of this potent greenhouse gas to the atmosphere. Incubation techniques with trace amounts of radiolabeled substrate (typically 14CH4) represent the most sensitive approach for methane oxidation rate measurements. Yet, radiotracer application can be performed in different ways, rendering the comparability of AOM rate measurements in field and laboratory investigations problematic. We compared four different 14CH4‐based short‐term incubation approaches to quantify methane turnover rates in lake sediments. Three of the applied methods yielded similar and reliable downcore rate profiles. They provided clear evidence for AOM with maximum rates of 15 nmol cm−3 d−1 at ~ 17 cm sediment depth. Using the short‐term slurry incubation (SL) method, however, we were unable to detect the AOM activity maximum that we observed with the other approaches. We hypothesize that changes in the microbial structure and disruption of physical interactions due to mixing of sediments negatively affected the activity of AOM communities and longer incubation times are necessary to enhance the sensitivity of this approach. Minor variabilities in rate measurement that we found in the non‐SL incubations may be related to small‐scale sediment heterogeneity, differential partial methane loss during sample handling, and/or an uneven application of the radiotracer. Whole‐core incubations interfere the least with the in situ conditions, but the ultimate choice of the AOM rate measurement method will depend on the individual sampling requirements.

An Areal Assessment of Subseafloor Carbon Cycling in Cold Seeps and Hydrate-Bearing Areas in the Northern South China Sea

Gas hydrates, acting as a dynamic methane reservoir, store methane in the form of a solid phase under high-pressure and low-temperature conditions and release methane through the sediment column into seawater when they are decomposed. The seepage of methane-rich fluid (i.e., cold hydrocarbon seeps) fuels the chemosynthetic biota-inhabited surface sediments and represents the major pathway to transfer carbon from sediments to the water column. Generally, the major biogeochemical reactions related to carbon cycling in the anoxic marine sediments include organic matter degradation via sulfate reduction (OSR), anaerobic oxidation of methane (AOM), methanogenesis (ME), and carbonate precipitation (CP). In order to better understand the carbon turnover in the cold seeps and gas hydrate-bearing areas of the northern South China Sea (SCS), we collected geochemical data of 358 cores from published literatures and retrieved 37 cores and corresponding pore water samples from three areas of interest (i.e., Xisha, Dongsha, and Shenhu areas). Reaction-transport simulations indicate that the rates of organic matter degradation and carbonate precipitation are comparable in the three areas, while the rates of AOM vary over several orders of magnitude (AOM: 8.3-37.5 mmol·m-2·yr-1 in Dongsha, AOM: 12.4-170.6 mmol·m-2·yr-1 in Xisha, and AOM: 9.4-30.5 mmol·m-2·yr-1 in Shenhu). Both the arithmetical mean and interpolation mean of the biogeochemical processes were calculated in each area. Averaging these two mean values suggested that the rates of organic matter degradation in Dongsha (25.7 mmol·m-2·yr-1) and Xisha (25.1 mmol·m-2·yr-1) are higher than that in Shenhu (12 mmol·m-2·yr-1) and the AOM rate in Xisha (135.2 mmol·m-2·yr-1) is greater than those in Dongsha (27.8 mmol·m-2·yr-1) and Shenhu (17.5 mmol·m-2·yr-1). In addition, the rate of carbonate precipitation (32.3 mmol·m-2·yr-1) in Xisha is far higher than those of the other two regions (5.3 mmol·m-2·yr-1 in Dongsha, 5.8 mmol·m-2·yr-1 in Shenhu) due to intense AOM sustained by gas dissolution. In comparison with other cold seeps around the world, the biogeochemical rates in the northern SCS are generally lower than those in active continental margins and special environments (e.g., the Black sea) but are comparable with those in passive continental margins. Collectively, ~2.8 Gmol organic matter was buried and at least ~0.82 Gmol dissolved organic and inorganic carbon was diffused out of sediments annually. This may, to some extent, have an impact on the long-term deep ocean carbon cycle in the northern SCS.

To shake or not to shake: 13C-based evidence on anaerobic methane oxidation in paddy soil

The anaerobic oxidation of methane (AOM) removes most of the biologically produced methane (CH4) from marine ecosystems before it enters the atmosphere and thus mitigates greenhouse gas emissions. As compared to marine environments, surprisingly little is known about the role of AOM in terrestrial ecosystems. Particularly, how AOM controls the CH4 budget of paddy soils is unexplored, partly reflecting analytical difficulties in analyzing CH4 turnover. To date, the most commonly used method to study AOM in soils is in vitro incubation of microcosms with CH4 injection into the headspace with/without shaking of slurry. Shaking, however, introduces various errors and disturbances. Here we measured AOM in rice paddy soil using a new alternative approach that introduced 13C-labelled CH4 directly into soil slurry via a silicone tube without shaking. The results were compared to those obtained by the classical approaches (i.e., with and without tubes and/or shaking). In all batches, 13C enrichment of CO2 after 13CH4 injection clearly confirmed the occurrence of AOM in paddy soil. The cumulative AOM during 84 days reached 0.16–0.24 μg C g−1 dry soil without shaking, but it was 33–80% lower with shaking. Unexpectedly, the effect of silicone tubes on AOM was insignificant either with or without shaking, suggesting that the CH4 concentration in water (slurry) was not the main limiting factor for AOM. Without shaking, the controls without CH4 addition revealed a steady increase of CH4 in the headspace/tube, whereas the CH4 concentration in jars with shaking was constantly low during 59 days. This suggests that shaking inhibited methanogenesis. There was a strong linear correlation between the amount of CH4 oxidized and CH4 produced with shaking (R2 = 0.91), whereas without shaking this relationship followed a power growth regression. Based on the current and reported AOM rates, rough upscale to paddy soils in China showed recycling of ca. 2.0 Tg C of CH4 each year, making AOM a crucial terrestrial CH4 sink.

First evidence for cold-adapted anaerobic oxidation of methane in deep sediments of thermokarst lakes

Microbial decomposition of thawed permafrost carbon in thermokarst lakes leads to the release of ancient carbon as the greenhouse gas methane (CH4), yet potential mitigating processes are not understood. Here, we report δ13C–CH4 signatures in the pore water of a thermokarst lake sediment core that points towards in situ occurrence of anaerobic oxidation of methane (AOM). Analysis of the microbial communities showed a natural enrichment in CH4-oxidizing archaeal communities that occur in sediment horizons at temperatures near 0 °C. These archaea also showed high rates of AOM in laboratory incubations. Calculation of the stable isotopes suggests that 41 to 83% of in situ dissolved CH4 is consumed anaerobically. Quantification of functional genes (mcrA) for anaerobic methanotrophic communities revealed up to 6.7 ± 0.7 × 105 copy numbers g−1 wet weight and showed similar abundances to bacterial 16S rRNA gene sequences in the sediment layers with the highest AOM rates. We conclude that these AOM communities are fueled by CH4 produced from permafrost organic matter degradation in the underlying sediments that represent the radially expanding permafrost thaw front beneath the lake. If these communities are widespread in thermokarst environments, they could have a major mitigating effect on the global CH4 emissions.

Anaerobic Methane Oxidation in High-Arctic Alaskan Peatlands as a Significant Control on Net CH4 Fluxes

Terrestrial consumption of the potent greenhouse gas methane (CH4) is a critical aspect of the future climate, as CH4 concentrations in the atmosphere are projected to play an increasingly important role in global climate forcing. Anaerobic oxidation of methane (AOM) has only recently been considered a relevant control on methane fluxes from terrestrial systems. We performed in vitro anoxic incubations of intact peat from Utqiaġvik (Barrow), Alaska using stable isotope tracers. Our results showed an average potential AOM rate of 15.0 nmol cm3 h−1, surpassing the average rate of gross CH4 production (6.0 nmol cm3 h−1). AOM and CH4 production rates were positively correlated. While CH4 production was insensitive to additions of Fe(III), there was a depth:Fe(III) interaction in the kinetic reaction rate constant for AOM, suggestive of stimulation by Fe(III), particularly in shallow soils (<10 cm). We estimate AOM would consume 25–34% of CH4 produced under ambient conditions. Soil genetic surveys showed phylogenetic links between soil microbes and known anaerobic methanotrophs in ANME groups 2 and 3. These results suggest a prevalent role of AOM to net CH4 fluxes from Arctic peatland ecosystems, and a probable link with Fe(III)-reduction.

Carbon isotope exchange during anaerobic oxidation of methane (AOM) in sediments of the northeastern South China Sea

The major processes that determine the distribution of methane (CH4) in anoxic marine sediments are methanogenesis and the anaerobic oxidation of methane (AOM), with organoclastic sulfate reduction exerting an important secondary control. However, the factors leading to the distribution of stable carbon isotopes (δ13C) of CH4 are currently poorly understood, in particular the commonly-observed minimum in δ13C-CH4 at the sulfate-methane transition (SMT) where AOM rates reach maximum values. Conventional isotope systematics predict 13C-enrichment of CH4 in the SMT due to preferential 12CH4 consumption by AOM. Two hypotheses put forward to explain this discrepancy are the addition of 12C-enriched CH4 to porewaters by methanogenesis in close proximity to AOM, and enzymatically-mediated carbon isotope equilibrium between forward and backward AOM at low concentrations of sulfate. To examine this in more detail, field data including δ13C of CH4 and dissolved inorganic carbon (DIC) from the continental margin offshore southwestern Taiwan were simulated with a reaction-transport model. Model simulations showed that the minima in δ13C-CH4 and δ13C-DIC in the SMT could only be simulated with carbon isotope equilibrium during AOM. The potential for carbon cycling between methanogenesis and AOM in and just below the SMT was insignificant due to very low rates of methanogenesis. Backward AOM also gives rise to a pronounced kink in the δ13C-DIC profile several meters below the SMT that has been observed in previous studies. We suggest that this kink marks the true base of the SMT where forward and backward AOM are operating at very low rates, possibly sustained by cryptic sulfur cycling or barite dissolution.

Electron shuttling mediated by humic substances fuels anaerobic methane oxidation and carbon burial in wetland sediments

Key pathways for the anaerobic oxidation of methane (AOM) have remained elusive, particularly in organic rich ecosystems. In this work, the occurrence of AOM driven by humus-catalyzed dissimilatory iron reduction was investigated in sediments from a coastal mangrove swamp. Anoxic sediment incubations supplied with both goethite (α-FeOOH) and leonardite (humic substances (HS)) displayed an average AOM rate of 10.7 ± 0.8 μmol CH4 cm−3 day−1, which was 7 and 3 times faster than that measured in incubations containing only goethite or HS, respectively. Additional incubations performed with 13C-methane displayed Pahokee Peat HS-mediated carbonate precipitation linked to 13CH4 oxidation and ferrihydrite reduction (~1.3 μmol carbonate cm−3 day−1). These results highlight the role of HS on mitigating greenhouse gases released from wetlands, not only by mediating the AOM process, but also by enhancing carbon sequestration as inert minerals (calcite, aragonite and siderite).

Coupled methane and nitrous oxide biotransformation in freshwater wetland sediment microcosms

Anaerobic oxidation of methane (AOM) coupled to denitrification is becoming the focus of scientific inquiry due to its potential contribution to global carbon and nitrogen cycles. AOM has been previously reported to proceed with nitrate (NO3−) or nitrite (NO2−). However, little research has been conducted on the simultaneous use of methane (CH4) and nitrous oxide (N2O). Here, coupled CH4 and N2O biotransformation in a freshwater wetland sediment was obtained in a 7-day anaerobic sediment incubation assay. The significant CO2 accumulation and decrease of CH4 emission in sediment microcosms was attributed to two mechanisms: inhibition of methanogenesis and N2O-dependent AOM. To further confirm the coupled CH4 and N2O transformation, a 13C-labelled stable isotope tracer assay after anaerobic incubation was conducted with N2O and/or CH4 amendments. The N2O-dependent AOM rate was 3.41 ± 0.13 nmol CO2 g−1 dry sediment·day−1. According to metagenomic analysis, addition of N2O stimulated AOM by increasing the activity and abundance of methanotrophic bacteria and by increasing enzymatic activities in the electron transport chain. Based on these results, we propose coupled CH4 and N2O biotransformation in the sediment microcosms for the first time, carried out by unidentified methanotroph(s) via intra‑oxygen produced in the presence of N2O. Such a process has the potential to reduce the emission of two highly potent greenhouse gases and makes a significant contribution to the link of global carbon and nitrogen cycles in anoxic environments.

Enrichment of ANME-2 dominated anaerobic methanotrophy from cold seep sediment in an external ultrafiltration membrane bioreactor.

Anaerobic oxidation of methane (AOM) coupled to sulfate reduction is a microbially mediated unique natural phenomenon with an ecological relevance in the global carbon balance and potential application in biotechnology. This study aimed to enrich an AOM performing microbial community with the main focus on anaerobic methanotrophic archaea (ANME) present in sediments from the Ginsburg mud volcano (Gulf of Cadiz), a known site for AOM, in a membrane bioreactor (MBR) for 726 days at 22 (± 3)°C and at ambient pressure. The MBR was equipped with a cylindrical external ultrafiltration membrane, fed a defined medium containing artificial seawater and operated at a cross flow velocity of 0.02 m/min. Sulfide production with simultaneous sulfate reduction was in equimolar ratio between days 480 and 585 of MBR operation, whereas methane consumption was in oscillating trend. At the end of the MBR operation (day 726), the enriched biomass was incubated with 13C labeled methane, 13C labeled inorganic carbon was produced and the AOM rate based on 13C-inorganic carbon was 1.2μmol/(gdwd). Microbial analysis of the enriched biomass at 400 and 726 days of MBR operation showed that ANME-2 and Desulfosarcina type sulfate reducing bacteria were enriched in the MBR, which formed closely associated aggregates. The major relevance of this study is the enrichment of an AOM consortium in a MBR system which can assist to explore the ecophysiology of ANME and provides an opportunity to explore the potential application of AOM.

U-Th chronology and formation controls of methane-derived authigenic carbonates from the Hola trough seep area, northern Norway

We investigated methane-derived authigenic carbonate (MDAC) crusts and nodules from a cold seep site on the northern Norwegian continental shelf in ca. 220m water depth to determine the timing and mode of their formation. Gas bubbling observed during remotely operated vehicle (ROV)-assisted sampling of MDAC crusts revealed ongoing seep activity. Authigenic carbonates were present as crusts on the seafloor and as centimetre-size carbonate-cemented nodules at several intervals within an adjacent sediment core. Aragonite-dominated mineralogy of the MDAC crusts suggests formation close to the seafloor at higher rates of sulphate-dependent anaerobic oxidation of methane (AOM). In contrast, dolomite-cemented nodules are consistent with the formation at the sulphate-methane-transition zone deeper within the sediment at lower rates of AOM. The δ13C-carbonate values of bulk rock and of micro-drilled aragonite samples vary between −22.2‰ and −34.6‰ (VPDB). We interpret the carbon in aragonite to be mainly derived from the anaerobic oxidation of thermogenic methane, with a minor contribution from seawater dissolved inorganic carbon (DIC). AOM activity is supported by high concentrations of AOM-related biomarkers of archaea (archaeol and 2-sn-hydroxyarchaeol) and sulphate-reducing bacteria (iso and anteiso-C15:0 fatty acids) in the crusts. The dolomite nodules exhibit higher δ13C-carbonate values (−12‰ VPDB) suggesting a smaller amount of methane-derived carbon, presumably due to the contribution of DIC migrating from depth, and lower AOM rates. The latter is supported by orders of magnitude lower concentrations of archaeol and sn-2-hydroxyarchaeol in the sediment interval containing the largest dolomite nodules. δ18O values of pure aragonite samples and dolomite nodules indicate the precipitation of carbonate close to isotopic equilibrium with seawater and no influence of gas hydrate-derived water. U-Th dating of two MDAC crusts shows that they formed between 1.61±0.02 and 4.39±1.63ka BP and between 2.65±0.02 and 4.32±0.08ka BP. We infer both a spatial and temporal change in methane flux and related MDAC formation at this seep site. These changes might be caused by regional seismic events that can affect pore pressure or re-activation of migration pathways thus facilitating fluid flow from deep sources towards the seabed.

A quantitative assessment of methane cycling in Hikurangi Margin sediments (New Zealand) using geophysical imaging and biogeochemical modeling

AbstractTakahe seep, located on the Opouawe Bank, Hikurangi Margin, is characterized by a well‐defined subsurface seismic chimney structure ∼80,500 m2 in area. Subseafloor geophysical data based on acoustic anomaly layers indicated the presence of gas hydrate and free gas layers within the chimney structure. Reaction‐transport modeling was applied to porewater data from 11 gravity cores to constrain methane turnover rates and benthic methane fluxes in the upper 10 m. Model results show that methane dynamics were highly variable due to transport and dissolution of ascending gas. The dissolution of gas (up to 3761 mmol m−2 yr−1) dwarfed the rate of methanogenesis within the simulated sediment column (2.6 mmol m−2 yr−1). Dissolved methane is mainly consumed by anaerobic oxidation of methane (AOM) at the base of the sulfate reduction zone and trapped by methane hydrate formation below it, with maximum rates in the central part of the chimney (946 and 2420 mmol m−2 yr−1, respectively). A seep‐wide methane budget was constrained by combining the biogeochemical model results with geophysical data and led to estimates of AOM rates, gas hydrate formation, and benthic dissolved methane fluxes of 3.68 × 104 mol yr−1, 73.85 × 104 mol yr−1, and 1.19 × 104 mol yr−1, respectively. A much larger flux of methane probably escapes in gaseous form through focused bubble vents. The approach of linking geochemical model results with spatial geophysical data put forward here can be applied elsewhere to improve benthic methane turnover rates from limited single spot measurements to larger spatial scales.

Anaerobic oxidation of methane alters sediment records of sulfur, iron and phosphorus in the Black Sea

Abstract. The surface sediments in the Black Sea are underlain by extensive deposits of iron (Fe)-oxide-rich lake sediments that were deposited prior to the inflow of marine Mediterranean Sea waters ca. 9000 years ago. The subsequent downward diffusion of marine sulfate into the methane-bearing lake sediments has led to a multitude of diagenetic reactions in the sulfate-methane transition zone (SMTZ), including anaerobic oxidation of methane (AOM) with sulfate. While the sedimentary cycles of sulfur (S), methane and Fe in the SMTZ have been extensively studied, relatively little is known about the diagenetic alterations of the sediment record occurring below the SMTZ.Here we combine detailed geochemical analyses of the sediment and porewater with multicomponent diagenetic modeling to study the diagenetic alterations below the SMTZ at two sites in the western Black Sea. We focus on the dynamics of Fe, S and phosphorus (P), and demonstrate that diagenesis has strongly overprinted the sedimentary burial records of these elements. In line with previous studies in the Black Sea, we show that sulfate-mediated AOM substantially enhances the downward diffusive flux of sulfide into the deep limnic deposits. During this downward sulfidization, Fe oxides, Fe carbonates and Fe phosphates (e.g., vivianite) are converted to sulfide phases, leading to an enrichment in solid-phase S and the release of phosphate to the porewater. Below the sulfidization front, high concentrations of dissolved ferrous Fe (Fe2+) lead to sequestration of downward-diffusing phosphate as authigenic vivianite, resulting in a transient accumulation of total P directly below the sulfidization front.Our model results further demonstrate that downward-migrating sulfide becomes partly re-oxidized to sulfate due to reactions with oxidized Fe minerals, fueling a cryptic S cycle and thus stimulating slow rates of sulfate-driven AOM ( ∼ 1–100 pmol cm−3 d−1) in the sulfate-depleted limnic deposits. However, this process is unlikely to explain the observed release of dissolved Fe2+ below the SMTZ. Instead, we suggest that besides organoclastic Fe oxide reduction and reactivation of less reactive Fe oxides by methanogens, AOM coupled to the reduction of Fe oxides may also provide a possible mechanism for the high concentrations of Fe2+ in the porewater at depth. Our results reveal that methane plays a key role in the diagenetic alterations of Fe, S and P records in Black Sea sediments. The downward sulfidization into the limnic deposits is enhanced through sulfate-driven AOM with sulfate, and AOM with Fe oxides may provide a deep source of dissolved Fe2+ that drives the sequestration of P in vivianite below the sulfidization front.