Anaerobic Oxidation Of Methane Rates Research Articles

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.

Biogeochemical and 16S rRNA gene sequence evidence supports a novel mode of anaerobic methanotrophy in permanently ice‐covered Lake Fryxell, Antarctica

AbstractLake Fryxell, McMurdo Dry Valleys, Antarctica contains a constantly cold water column and perennial ice‐cover. Although carbon and sulfur cycling in this amictic lake have been studied previously, a paired investigation of 16S rRNA gene based microbial diversity and geochemistry of Lake Fryxell is lacking. Here, we used a combination of radiotracer‐based rate measurements, geochemical measurements, and molecular microbial community analysis to investigate the anaerobic oxidation of methane (AOM) and associated processes in Lake Fryxell. The results show that while AOM and sulfate reduction appear coupled in the upper regions of the anoxic water column, in deep anoxic waters, where AOM rates are highest, sulfate is unlikely to be the electron acceptor for AOM. Despite significant rates of AOM in these waters, no putative AOM‐associated Archaea or Bacteria were observed. Due to a lack of documented AOM electron acceptors and putative ANMEs, we suggest novel modes of AOM dominate in this extreme environment. First, the notable abundance of the bacterial genus Dehalococcoides suggests that reductive dehalogenation could fuel AOM. Further, taxa of the candidate phylum OP9, the Atribacteria, and the Bathyarchaeota (formerly known as the Miscellaneous Crenarchaeotal Group) both commonly observed at cold methane‐seeps globally, may mediate AOM, possibly using humic acids as electron shuttles, in Lake Fryxell.

Efficiency and adaptability of the benthic methane filter at Quepos Slide cold seeps, offshore of Costa Rica

Abstract. Large amounts of methane are delivered by fluids through the erosive forearc of the convergent margin offshore of Costa Rica and lead to the formation of cold seeps at the sediment surface. Besides mud extrusion, numerous cold seeps are created by landslides induced by seamount subduction or fluid migration along major faults. Most of the dissolved methane migrating through the sediments of cold seeps is oxidized within the benthic microbial methane filter by anaerobic oxidation of methane (AOM). Measurements of AOM and sulfate reduction as well as numerical modeling of porewater profiles revealed a highly active and efficient benthic methane filter at the Quepos Slide site, a landslide on the continental slope between the Nicoya and Osa Peninsula. Integrated areal rates of AOM ranged from 12.9 ± 6.0 to 45.2 ± 11.5 mmol m−2 d−1, with only 1 to 2.5 % of the upward methane flux being released into the water column. Additionally, two parallel sediment cores from Quepos Slide were used for in vitro experiments in a recently developed sediment-flow-through (SLOT) system to simulate an increased fluid and methane flux from the bottom of the sediment core. The benthic methane filter revealed a high adaptability whereby the methane oxidation efficiency responded to the increased fluid flow within ca. 170 d. To our knowledge, this study provides the first estimation of the natural biogeochemical response of seep sediments to changes in fluid flow.

High rates of anaerobic methane oxidation in freshwater wetlands reduce potential atmospheric methane emissions

The role of anaerobic oxidation of methane (AOM) in wetlands, the largest natural source of atmospheric methane, is poorly constrained. Here we report rates of microbially mediated AOM (average rate=20 nmol cm(-3) per day) in three freshwater wetlands that span multiple biogeographical provinces. The observed AOM rates rival those in marine environments. Most AOM activity may have been coupled to sulphate reduction, but other electron acceptors remain feasible. Lipid biomarkers typically associated with anaerobic methane-oxidizing archaea were more enriched in (13)C than those characteristic of marine systems, potentially due to distinct microbial metabolic pathways or dilution with heterotrophic isotope signals. On the basis of this extensive data set, AOM in freshwater wetlands may consume 200 Tg methane per year, reducing their potential methane emissions by over 50%. These findings challenge precepts surrounding wetland carbon cycling and demonstrate the environmental relevance of an anaerobic methane sink in ecosystems traditionally considered strong methane sources.

Constraining silica diagenesis in methane-seep deposits

Silicified fossils and authigenic silica are common in ancient seep limestones. Silicification of calcareous fossils facilitates the preservation of even fine details and is therefore of great interest to paleontologists, permitting a reliable taxonomic identification of the chemosynthesis-based taxa that lived at hydrocarbon seeps. Four methane-seep limestones of Paleozoic, Mesozoic, and Cenozoic age with abundant silica phases are compared in this study; one, an Eocene seep deposit on the north shore of the Columbia River at Knappton, western Washington State, USA, is described for the first time. Its lithology and fabrics, negative δ13Ccarbonate values as low as −27.6‰, and 13C-depleted biomarkers of archaea involved in the anaerobic oxidation of methane (AOM) reveal that the carbonate rock formed at a methane seep. The background sediments of the studied Phanerozoic seep limestones contain abundant siliceous microfossils, radiolarian tests in case of the Carboniferous Dwyka Group deposits from Namibia and the Triassic Graylock Butte deposits from Oregon (USA), as well as diatom frustules in case of the Eocene Knappton limestone and an Oligocene seep deposit from the Lincoln Creek Formation (Washington State, USA). These microfossils are regarded as the source of dissolved silica, causing silicification and silica precipitation. Silica cements formed after AOM-derived cements ceased to precipitate but before equant calcite formed. Numerical experiments using the computer code PHREEQC confirmed that (1) AOM increases the pH of pore waters and that (2) this pH increase subsequently mobilizes biogenic silica, (3) followed by the re-precipitation of the dissolved silica in the periphery of the AOM hotspot. The experiments revealed that degassing of carbon dioxide has the potential to significantly increase the local pH of pore waters, exerting an even stronger control on the local pH and silica dissolution than the rate of AOM alone.

Stratified community responses to methane and sulfate supplies in mud volcano deposits: insights from an in vitro experiment.

Numerous studies on marine prokaryotic communities have postulated that a process of anaerobic oxidation of methane (AOM) coupled with sulfate reduction (SR) is the main methane sink in the world's oceans. AOM has also been reported in the deep biosphere. But the responses of the primary microbial players in eliciting changes in geochemical environments, specifically in methane and sulfate supplies, have yet to be fully elucidated. Marine mud volcanoes (MVs) expel a complex fluid mixture of which methane is the primary component, forming an environment in which AOM is a common phenomenon. In this context, we attempted to identify how the prokaryotic community would respond to changes in methane and sulfate intensities, which often occur in MV environments in the form of eruptions, diffusions or seepage. We applied an integrated approach, including (i) biochemical surveys of pore water originated from MV, (ii) in vitro incubation of mud breccia, and (iii) prokaryotic community structure analysis. Two distinct AOM regions were clearly detected. One is related to the sulfate methane transition zone (SMTZ) at depth of 30–55 cm below the sea floor (bsf); the second is at 165–205 cm bsf with ten times higher rates of AOM and SR. This finding contrasts with the sulfide concentrations in pore waters and supports the suggestion that potential AOM activity below the SMTZ might be an important methane sink that is largely ignored or underestimated in oceanic methane budget calculations. Moreover, the incubation conditions below the SMTZ favor the growth of methanotrophic archaeal group ANME-2 compared to ANME-1, and promote the rapid growth and high diversity of bacterial communities. These incubation conditions also promote the increase of richness in bacterial communities. Our results provide direct evidence of the mechanisms by which deep AOM processes can affect carbon cycling in the deep biosphere and global methane biochemistry.

More evidence that anaerobic oxidation of methane is prevalent in soils: Is it time to upgrade our biogeochemical models?

Estimating future fluxes of CH4 between land and atmosphere requires well-conceived process-based biogeochemical models. Current models do not represent the anaerobic oxidation of methane (AOM) in land surface soils, in spite of increasing evidence that this process is widespread. Our objective was to determine whether AOM, or potential AOM, commonly occurs in 20 hydromorphic soils spanning a wide range of chemical properties. Bulk soil samples were collected under shallow water near the shoreline of 15 recently drained fish ponds in southern Bohemia (Czech Republic), as well as from below the water table at 3 peatland locations in northeast Scotland and 2 acid sulfate soils on the southern coast of Finland. Each soil slurry was incubated under both oxic and anoxic conditions, with or without the addition of alternative electron acceptors (SO42− and NO3−) or H2PO4−. Here, “oxic” and “anoxic” conditions refer to anoxic soil respectively incubated in a headspace containing air or argon. Using the isotope dilution method, we determined the gross production and oxidation rates of CH4 after 2 days incubation under oxic headspace conditions, and after 2, 21 and 60 days incubation under anoxic conditions. Large differences in net CH4 fluxes were observed between soil types and between incubation conditions. AOM was detected in each of the 20 bulk soil samples, which spanned >6 pH units and 2 orders of magnitude in organic C content. Significant positive relationships were found between AOM and gross CH4 production rates under anoxic conditions, resulting in AOM rates that were sometimes higher than CH4 oxidation rates under oxic headspace conditions. There was no relationship between net and gross CH4 production rates, such that 2 soil types could display similar low net rates, yet conceal very large differences in gross rates. The effects of alternative electron acceptors on AOM were idiosyncratic and resulted in no net trend. We did find, however, a negative effect of SO42− and H2PO4− on gross CH4 production rates under anoxic and oxic conditions respectively. Under oxic headspace conditions, CH4 oxidation was related to soil organic C content. Taken collectively, our results suggest that AOM, or potential AOM, is prevalent over a wide range of soil types, that AOM may contribute substantially to CH4 oxidation in soils, and that AOM in soils should be integrated to current process-based CH4 cycling models.

Pore-water chemistry of sediment cores off Mahanadi Basin, Bay of Bengal: Possible link to deep seated methane hydrate deposit

Organoclastic degradation and anaerobic oxidation of methane (AOM) are known to influence sulfate, methane and bicarbonate concentrations of sediment pore-waters. In this work we have analyzed the pore-fluid composition of three piston cores (36–39 m long) collected from water depths ranging from 1429 to 1691 m. We attribute the observed linear sulfate concentration profiles and (ΔCa + ΔAlk)/ΔSO42− ratios dominantly to anaerobic oxidation of methane (AOM) induced sulfate consumption. The gas rich layers just below the base of hydrate stability zone (BGHSZ) is the possible source of the enhanced diffusive flux of biogenic methane (δ13CCH4 ranging from −99.7 to −106.3‰ VPDB). Occurrences of disseminated gas hydrate in the Mahanadi Basin within the hydrate stability zone (210–220 m thick) supports the link between linear sulfate profile, high rate of AOM and hydrate occurrence.

Relating sulfate and methane dynamics to geology: Accretionary prism offshore SW Taiwan

Geochemical data (CH4, SO42−, I−, Cl−, particulate organic carbon (POC), δ13C‐CH4, and δ13C‐CO2) are presented from the upper 30 m of marine sediment on a tectonic submarine accretionary wedge offshore southwest Taiwan. The sampling stations covered three ridges (Tai‐Nan, Yung‐An, and Good Weather), each characterized by bottom simulating reflectors, acoustic turbidity, and different types of faulting and anticlines. Sulfate and iodide concentrations varied little from seawater‐like values in the upper 1–3 m of sediment at all stations; a feature that is consistent with irrigation of seawater by gas bubbles rising through the soft surface sediments. Below this depth, sulfate was rapidly consumed within 5–10 m by anaerobic oxidation of methane (AOM) at the sulfate‐methane transition. Carbon isotopic data imply a mainly biogenic methane source. A numerical transport‐reaction model was used to identify the supply pathways of methane and estimate depth‐integrated turnover rates at the three ridges. Methane gas ascending from deep layers, facilitated by thrusts and faults, was by far the dominant term in the methane budget at all sites. Differences in the proximity of the sampling sites to the faults and anticlines mainly accounted for the variability in gas fluxes and depth‐integrated AOM rates. By comparison, methane produced in situ by POC degradation within the modeled sediment column was unimportant. This study demonstrates that the geochemical trends in the continental margins offshore SW Taiwan are closely related to the different geological settings.

A method for the calculation of anaerobic oxidation of methane rates across regional scales: an example from the Belt Seas and The Sound (North Sea–Baltic Sea transition)

Estimating the amount of methane in the seafloor globally as well as the flux of methane from sediments toward the ocean–atmosphere system are important considerations in both geological and climate sciences. Nevertheless, global estimates of methane inventories and rates of methane production and consumption through anaerobic oxidation in marine sediments are very poorly constrained. Tools for regionally assessing methane formation and consumption rates would greatly increase our understanding of the spatial heterogeneity of the methane cycle as well as help constrain the global methane budget. In this article, an algorithm for calculating methane consumption rates in the inner shelf is applied to the gas-rich sediments of the Belt Seas and The Sound (North Sea–Baltic Sea transition). It is based on the depth of free gas determined by hydroacoustic techniques and the local methane solubility concentration. Due to the continuous nature of shipboard hydroacoustic measurements, this algorithm captures spatial heterogeneities in methane fluxes better than geochemical analyses of point sources such as observational/sampling stations. The sensibility of the algorithm with respect to the resolution of the free gas depth measurements (2 m vs. 50 cm) is proven of minor importance (a discrepancy of <10%) for a small part of the study area. The algorithm-derived anaerobic methane oxidation rates compare well with previous measured and modeling studies. Finally, regional results reveal that contemporary anaerobic methane oxidation in worldwide inner-shelf sediments may be an order of magnitude lower (ca. 0.24 Tmol year–1) than previous estimates (4.6 Tmol year–1). These algorithms ultimately help improve regional estimates of anaerobic oxidation of methane rates.

Impact of electron acceptor availability on the anaerobic oxidation of methane in coastal freshwater and brackish wetland sediments

Methane, a powerful greenhouse gas, is both produced and consumed in anoxic coastal sediments via microbial processes. Although the anaerobic oxidation of methane (AOM) is almost certainly an important process in coastal freshwater and salt marsh sediments, the factors that control the rates and pathways of AOM in these habitats are poorly understood. Here, we present the first direct measurements of AOM activity in freshwater (0PSU) and brackish (25PSU) wetland sediments. Despite disparate sulfate concentrations, both environments supported substantial rates of AOM. Higher sulfate reduction (SR) rates were measured in the freshwater site and SR at both sites was of sufficient magnitude to support the observed AOM activity. Laboratory incubations of freshwater and brackish tidal, wetland sediments amended with either nothing [control], sulfate, nitrate, manganese oxide (birnessite) or iron oxide (ferrihydrite) and supplied with a methane headspace were used to evaluate the impact(s) of electron acceptor availability on potential AOM rates. Maximum AOM rates in brackish slurries occurred in the sulfate amendments. In contrast, addition of sulfate and several possible electron acceptors to the freshwater slurries decreased AOM rates relative to the control. High ratios of AOM activity relative to SR activity in the nitrate, birnessite, and ferrihydrite treatments of both the brackish and freshwater slurries provided evidence of AOM decoupled from SR. This study demonstrates that both freshwater and brackish coastal wetland sediments support considerable rates of anaerobic methanotrophy and provides evidence for sulfate-independent AOM that may be coupled to nitrate, iron, or manganese reduction in both environments.

Anaerobic oxidation of methane in an iron‐rich Danish freshwater lake sediment

Freshwater systems are identified as one of the main natural methane sources, but little is known about the importance of anaerobic oxidation of methane (AOM) in these systems. We investigated AOM in a lake sediment characterized by a high reactive iron content, normal sulfate concentrations in the bottom water (∼ 250 µmol L−1), and a relatively deep sulfate penetration of ∼ 14 cm, which facilitated the spatial resolution of the zones of methane production and consumption. Methane concentrations, δ13C methane profiles, and directly measured and modeled AOM rates all consistently demonstrated methane consumption throughout the anoxic, nitrate‐free, Fe(III)‐ and sulfate‐containing zone, oxidizing ∼ 90% of the diffusive methane flux. Thus, the concentration gradient of methane was steepest at the base of the Fe(III) and sulfate zone and decreased strongly toward the sediment surface; while δ13CH4 increased from &lt; −80‰ in the methanogenic zone to −48‰ in the surface sediment. Direct measurements demonstrated AOM activity throughout the Fe(III) and sulfate zone. AOM rates peaked at sulfate concentrations below 3 µmol L−1, which suggests a possible coupling of AOM to the reduction of more crystalline Fe(III) oxides. Alternatively, AOM could be coupled to sulfate reduction, which was in turn supported by a cryptic sulfur cycle coupled to Fe(III) reduction. Our results show that AOM can substantially reduce methane emission from freshwater sediments, and the finding of AOM at sulfate concentrations &lt; 3 µmol L−1 suggests that AOM could be of greater importance in freshwater systems, and in ancient low‐sulfate oceans, than was previously appreciated.

The evolution of early diagenetic signals in Bering Sea subseafloor sediments in response to varying organic carbon deposition over the last 4.3 Ma

Transient pore-water and solid-phase signatures in deep subseafloor marine sediments, resulting from changes in both the amount and the quality of the organic matter input, are common but often difficult to interpret. We combined high-resolution pore-water and solid-phase data from Integrated Ocean Drilling Program (IODP) Expedition 323 Site U1341 (Bowers Ridge, Bering Sea) with inverse reaction-transport modeling to examine the evolution and potential preservation of diagenetic signals in these deep subseafloor sediments. We explore how these signals reflect major changes in the deposition and reactivity of organic matter to the seafloor at Bowers Ridge. Results of the inverse model approach reveal that 2.51–2.58Ma ago a high deposition flux of extremely labile organic matter, probably linked to increased surface water primary productivity, affected this site. Associated elevated organoclastic sulfate reduction rates facilitated low sulfate concentrations, the onset of methanogenesis, and consequently sulfate reduction coupled to the anaerobic oxidation of methane (AOM). Sulfate depletion caused the dissolution of biogenic barite reflected by a sedimentary interval with low Ba/Al ratios. Two sulfate–methane transition zones (SMTZs) evolved where high rates of AOM controlled sulfate consumption which was sustained by the influx of sulfate from seawater above and a deep source below. The positions of both SMTZs shifted non-synchronously over the subsequent ∼130,000yrs, until methanogenesis and AOM declined. The present-day sulfate concentration and sulfur isotope profiles still reflect the impact of the reactive organic matter pulse. They also record a period of very low reactive organic matter deposition during the middle to late Pleistocene, probably linked to very low primary productivity, resulting in little microbial carbon turnover in the sediment. Our study shows that combining biogeochemical signatures recorded in the solid-phase of deep subseafloor sediments with the analysis of transient pore-water signals by inverse reaction-transport modeling yields new insights into past deep biosphere processes and the paleoproductivity of marine basins.

Net Methane Oxidation Performance of Anaerobic Sewage Sludge

The anaerobic oxidation of methane (AOM) in anaerobic sewage sludge was characterized. The net methane oxidation was observed in samples amended with methane plus sulfate or with methane alone, whereas methane formation was observed in the samples without methane, indicating that methane oxidation and formation occurred simultaneously. The ratio of the net methane oxidation rate to H2S formation was 100:1, suggesting that the AOM was not closely associated with sulfate reduction in the anaerobic sludge. The net AOM was positively associated with the methane concentration and sludge dilution ratio. However, the rate of AOM was negatively correlated with organic substrate (acetate) concentration. Therefore, the production and oxidation of methane could be controlled by environmental conditions and dissolved organic compounds in the bulk solution.

Anaerobic methane oxidation in metalliferous hydrothermal sediments: influence on carbon flux and decoupling from sulfate reduction

The anaerobic oxidation of methane (AOM) is a globally significant sink that regulates methane flux from sediments into the oceans and atmosphere. Here we examine mesophilic to thermophilic AOM in hydrothermal sediments recovered from the Middle Valley vent field, on the Juan de Fuca Ridge. Using continuous-flow sediment bioreactors and batch incubations, we characterized (i) the degree to which AOM contributes to net dissolved inorganic carbon flux, (ii) AOM and sulfate reduction (SR) rates as a function of temperature and (iii) the distribution and density of known anaerobic methanotrophs (ANMEs). In sediment bioreactors, inorganic carbon stable isotope mass balances results indicated that AOM accounted for between 16% and 86% of the inorganic carbon produced, underscoring the role of AOM in governing inorganic carbon flux from these sediments. At 90°C, AOM occurred in the absence of SR, demonstrating a striking decoupling of AOM from SR. An abundance of Fe(III)-bearing minerals resembling mixed valent Fe oxides, such as green rust, suggests the potential for a coupling of AOM to Fe(III) reduction in these metalliferous sediments. While SR bacteria were only observed in cooler temperature sediments, ANMEs allied to ANME-1 ribotypes, including a putative ANME-1c group, were found across all temperature regimes and represented a substantial proportion of the archaeal community. In concert, these results extend and reshape our understanding of the nature of high temperature methane biogeochemistry, providing insight into the physiology and ecology of thermophilic anaerobic methanotrophy and suggesting that AOM may play a central role in regulating biological dissolved inorganic carbon fluxes to the deep ocean from the organic-poor, metalliferous sediments of the global mid-ocean ridge hydrothermal vent system.

Authigenic carbonates from active methane seeps offshore southwest Africa

The southwest African continental margin is well known for occurrences of active methane-rich fluid seeps associated with seafloor pockmarks at water depths ranging broadly from the shelf to the deep basins, as well as with high gas flares in the water column, gas hydrate accumulations, diagenetic carbonate crusts and highly diverse benthic faunal communities. During the M76/3a expedition of R/V METEOR in 2008, gravity cores recovered abundant authigenic carbonate concretions from three known pockmark sites—Hydrate Hole, Worm Hole, the Regab pockmark—and two sites newly discovered during that cruise, the so-called Deep Hole and Baboon Cluster. The carbonate concretions were commonly associated with seep-benthic macrofauna and occurred within sediments bearing shallow gas hydrates. This study presents selected results from a comprehensive analysis of the mineralogy and isotope geochemistry of diagenetic carbonates sampled at these five pockmark sites. The oxygen isotope stratigraphy obtained from three cores of 2–5 m length indicates a maximum age of about 60,000–80,000 years for these sediments. The authigenic carbonates comprise mostly magnesian calcite and aragonite, associated occasionally with dolomite. Their very low carbon isotopic compositions (–61.0 < δ13C ‰ V-PDB < –40.1) suggest anaerobic oxidation of methane (AOM) as the main process controlling carbonate precipitation. The oxygen isotopic signatures (+2.4 < δ18O ‰ V-PDB < +6.2) lie within the range in equilibrium under present-day/interglacial to glacial conditions of bottom seawater; alternatively, the most positive δ18O values might reflect the contribution of 18O-rich water from gas hydrate decomposition. The frequent occurrence of diagenetic gypsum crystals suggests that reduced sulphur (hydrogen sulphide, pyrite) from sub-seafloor sediments has been oxidized by oxygenated bottom water. The acidity released during this process can potentially induce the dissolution of carbonate, thereby providing enough Ca2+ ions for pore solutions to reach gypsum saturation; this is thought to be promoted by the bio-irrigation and burrowing activity of benthic fauna. The δ18O–δ13C patterns identified in the authigenic carbonates are interpreted to reflect variations in the rate of AOM during the last glacial–interglacial cycle, in turn controlled by variably strong methane fluxes through the pockmarks. These results complement the conclusions of Kasten et al. in this special issue, based on authigenic barite trends at the Hydrate Hole and Worm Hole pockmarks which were interpreted to reflect spatiotemporal variations in AOM related to subsurface gas hydrate formation–decomposition.

Anaerobic oxidation of methane in tropical and boreal soils: Ecological significance in terrestrial methane cycling

Anaerobic oxidation of methane (AOM) is a considerable sink for the greenhouse gas methane (CH4) in marine systems, but the importance of this process in terrestrial systems is less clear. Lowland boreal soils and wet tropical soils are two hot spots for CH4 cycling, yet AOM has been essentially uncharacterized in these systems. We investigated AOM in soils from sites in Alaska and Puerto Rico. Isotope tracers were utilized in vitro to enable the simultaneous quantification of CH4 production and consumption without use of biological inhibitors. Boreal peat soil and tropical mineral soil oxidized small but significant quantities of CH4 to CO2 under anoxic conditions (p &lt; 0.001). Potential AOM rates were 21 ± 2 nmol gdw−1 d−1 and 2.9 ± 0.5 nmol gdw−1 d−1 for the boreal and tropical soils, respectively. The addition of terminal electron acceptors (NO3−, Fe(III), and SO42−) inhibited AOM and methanogenesis in both soils. In all incubations, CH4 production occurred simultaneously with AOM, and CH4 production rates were always greater than AOM rates. There was a strong correlation between the quantity of CH4 produced and the amount of CH4 oxidized under anoxic conditions (Alaska: r = 0.875, p &lt; 0.0001; Puerto Rico: r = 0.817, p &lt; 0.0001). CH4 oxidation under anoxic conditions was biological and likely mediated by methanogenic archaea. While only a small percentage of the total CH4 produced in these soils was oxidized under anoxic conditions (0.3% and 0.8% for Alaskan and Puerto Rican Soils), this process is important to understand since it could play a measurable role in controlling net CH4 flux.

Carbon and sulfur back flux during anaerobic microbial oxidation of methane and coupled sulfate reduction.

Microbial degradation of substrates to terminal products is commonly understood as a unidirectional process. In individual enzymatic reactions, however, reversibility (reverse reaction and product back flux) is common. Hence, it is possible that entire pathways of microbial degradation are associated with back flux from the accumulating product pool through intracellular intermediates into the substrate pool. We investigated carbon and sulfur back flux during the anaerobic oxidation of methane (AOM) with sulfate, one of the least exergonic microbial catabolic processes known. The involved enzymes must operate not far from the thermodynamic equilibrium. Such an energetic situation is likely to favor product back flux. Indeed, cultures of highly enriched archaeal-bacterial consortia, performing net AOM with unlabeled methane and sulfate, converted label from (14)C-bicarbonate and (35)S-sulfide to (14)C-methane and (35)S-sulfate, respectively. Back fluxes reached 5% and 13%, respectively, of the net AOM rate. The existence of catabolic back fluxes in the reverse direction of net reactions has implications for biogeochemical isotope studies. In environments where biochemical processes are close to thermodynamic equilibrium, measured fluxes of labeled substrates to products are not equal to microbial net rates. Detection of a reaction in situ by labeling may not even indicate a net reaction occurring in the direction of label conversion but may reflect the reverse component of a so far unrecognized net reaction. Furthermore, the natural isotopic composition of the substrate and product pool will be determined by both the forward and back flux. This finding may have to be considered in the interpretation of stable isotope records.

Improved measurement of microbial activity in deep‐sea sediments at in situ pressure and methane concentration

A robust and convenient method was developed to evaluate rates of microbial activity in gas‐charged deepsea sediments at in situ hydrostatic pressure, temperature, and gas concentration. The method used a hydrostatic chamber to maintain high pressures of 50 bar and greater, and a modified Hungate tube and plunger to contain samples. This technique can be easily applied to quantifying rates of microbial processes sensitive to dissolved gas concentration (e.g., sulfate reduction, anaerobic methane oxidation, and methanogenesis) in high pressure, gas‐rich environments. Here, the method was used to determine rates of microbial activity in cold seep sediments from the Gulf of Mexico and the California coast. We measured rates of sulfate reduction (SR), anaerobic oxidation of methane (AOM), and methanogenesis (MOG) using radiotracer techniques. We compared in situ pressure and elevated methane concentration assays to traditional ex situ incubations at 1 bar using recovered (degassed) sediment. Methane concentrations were elevated in ex situ incubations to assess a substrate level effect. Upon the application of pressure, rates of AOM, SR, and MOG increased. AOM and MOG rates were more sensitive to methane addition than SR. Our results show that measuring rates of deep‐sea microbial activity at in situ pressure and gas concentrations is essential to quantify carbon flow in these environments accurately.

Impact of seasonal temperature and pressure changes on methane gas production, dissolution, and transport in unfractured sediments

A one‐dimensional reaction‐transport model is used to investigate the dynamics of methane gas in coastal sediments in response to intra‐annual variations in temperature and pressure. The model is applied to data from two shallow water sites in Eckernforde Bay (Germany) characterized by low and high rates of upward fluid advection. At both sites, organic matter is buried below the sulfate‐reducing zone to the methanogenic zone at sufficiently high rates to allow supersaturation of the pore water with dissolved methane and to form a free methane gas phase. The methane solubility concentration varies by similar magnitudes at both study sites in response to bottom water temperature changes and leads to pronounced peaks in the gas volume fraction in autumn when the methanic zone temperature is at a maximum. Yearly hydrostatic pressure variations have comparatively negligible effects on methane solubility. Field data suggest that no free gas escapes to the water column at any time of the year. Although the existence of gas migration cannot be substantiated by direct observation, a speculative mechanism for slow moving gas is proposed here. The model results reveal that free gas migrating upward into the undersaturated pore water will completely dissolve and subsequently be consumed above the free gas depth (FGD) by anaerobic oxidation of methane (AOM). This microbially mediated process maintains methane undersaturation above the FGD. Although the complexities introduced by seasonal changes in temperature lead to different seasonal trends for the depth‐integrated AOM rates and the FGD, both sites adhere to previously developed prognostic indicators for methane fluxes based on the FGD.