Two ~6 m long sediment cores were collected along the ~300 m isobath on the Alaskan-Beaufort continental margin. Both cores showed distinct sulfate-methane transition zones (SMTZ) at 105 and 120 cm below seafloor (cmbsf). Sulfate was not completely depleted below the SMTZ but remained between 30 and 500 µM. Sulfate reduction and anaerobic oxidation of methane (AOM) determined by radiotracer incubations were active throughout the methanogenic zone. Although a mass balance could not explain the source of sulfate below the SMTZ, geochemical profiles and correlation network analyses of biotic and abiotic data suggest a cryptic sulfur cycle involving iron, manganese and barite. Inhibition experiments with molybdate and 2-bromoethanesulfonate (BES) indicated decoupling of sulfate reduction and AOM and competition between sulfate reducers and methanogens for substrates. While correlation network analyses predicted coupling of AOM to iron reduction, the addition of manganese or iron did not stimulate AOM. Since none of the classical archaeal anaerobic methanotrophs (ANME) were abundant, the involvement of unknown or unconventional phylotypes in AOM is conceivable. The resistance of AOM activity to inhibitors implies deviation from conventional enzymatic pathways. This work suggests the classical redox cascade of electron acceptor utilization based on Gibbs energy yields

Abstract. Coastal seas may account for more than 75 % of global oceanic methane emissions. There, methane is mainly produced microbially in anoxic sediments from which it can escape to the overlying water column. Aerobic methane oxidation (MOx) in the water column acts as a biological filter, reducing the amount of methane that eventually evades to the atmosphere. The efficiency of the MOx filter is potentially controlled by the availability of dissolved methane and oxygen, as well as temperature, salinity, and hydrographic dynamics, and all of these factors undergo strong temporal fluctuations in coastal ecosystems. In order to elucidate the key environmental controls, specifically the effect of oxygen availability, on MOx in a seasonally stratified and hypoxic coastal marine setting, we conducted a 2-year time-series study with measurements of MOx and physico-chemical water column parameters in a coastal inlet in the south-western Baltic Sea (Eckernförde Bay). We found that MOx rates generally increased toward the seafloor, but were not directly linked to methane concentrations. MOx exhibited a strong seasonal variability, with maximum rates (up to 11.6 nmol L−1 d−1) during summer stratification when oxygen concentrations were lowest and bottom-water temperatures were highest. Under these conditions, 2.4–19.0 times more methane was oxidized than emitted to the atmosphere, whereas about the same amount was consumed and emitted during the mixed and oxygenated periods. Laboratory experiments with manipulated oxygen concentrations in the range of 0.2–220 µmol L−1 revealed a submicromolar oxygen optimum for MOx at the study site. In contrast, the fraction of methane–carbon incorporation into the bacterial biomass (compared to the total amount of oxidized methane) was up to 38-fold higher at saturated oxygen concentrations, suggesting a different partitioning of catabolic and anabolic processes under oxygen-replete and oxygen-starved conditions, respectively. Our results underscore the importance of MOx in mitigating methane emission from coastal waters and indicate an organism-level adaptation of the water column methanotrophs to hypoxic conditions.

Abstract. We studied the concurrence of methanogenesis and sulfate reduction in surface sediments (0–25 cm below sea floor) at six stations (70, 145, 253, 407, 990 and 1024 m) along the Peruvian margin (12° S). This oceanographic region is characterized by high carbon export to the seafloor creating an extensive oxygen minimum zone (OMZ) on the shelf, both factors that could favor surface methanogenesis. Sediments sampled along the depth transect traversed areas of anoxic and oxic conditions in the bottom-near water. Net methane production (batch incubations) and sulfate reduction (35S-sulfate radiotracer incubation) were determined in the upper 0–25 cm b.s.f. of multiple cores from all stations, while deep hydrogenotrophic methanogenesis (> 30 cm b.s.f., 14C-bicarbonate radiotracer incubation) was determined in two gravity cores at selected sites (78 and 407 m). Furthermore, stimulation (methanol addition) and inhibition (molybdate addition) experiments were carried out to investigate the relationship between sulfate reduction and methanogenesis.Highest rates of methanogenesis and sulfate reduction in the surface sediments, integrated over 0–25 cm b.s.f., were observed on the shelf (70–253 m, 0.06–0.1 and 0.5-4.7 mmol m−2 d−1, respectively), while lowest rates were discovered at the deepest site (1024 m, 0.03 and 0.2 mmol m−2 d−1, respectively). The addition of methanol resulted in significantly higher surface methanogenesis activity, suggesting that the process was mostly based on non-competitive substrates – i.e., substrates not used by sulfate reducers. In the deeper sediment horizons, where competition was probably relieved due to the decrease of sulfate, the usage of competitive substrates was confirmed by the detection of hydrogenotrophic activity in the sulfate-depleted zone at the shallow shelf station (70 m).Surface methanogenesis appeared to be correlated to the availability of labile organic matter (C ∕ N ratio) and organic carbon degradation (DIC production), both of which support the supply of methanogenic substrates. A negative correlation between methanogenesis rates and dissolved oxygen in the bottom-near water was not obvious; however, anoxic conditions within the OMZ might be advantageous for methanogenic organisms at the sediment-water interface.Our results revealed a high relevance of surface methanogenesis on the shelf, where the ratio between surface to deep (below sulfate penetration) methanogenic activity ranged between 0.13 and 105. In addition, methane concentration profiles indicated a partial release of surface methane into the water column as well as consumption of methane by anaerobic methane oxidation (AOM) in the surface sediment. The present study suggests that surface methanogenesis might play a greater role in benthic methane budgeting than previously thought, especially for fueling AOM above the sulfate–methane transition zone.

Abstract. Benthic microbial methanogenesis is a known source of methane in marine systems. In most sediments, the majority of methanogenesis is located below the sulfatereducing zone, as sulfate reducers outcompete methanogens for the major substrates hydrogen and acetate. The coexistence of methanogenesis and sulfate reduction has been shown before and is possible through the usage of noncompetitive substrates by methanogens such as methanol or methylated amines. However, knowledge about the magnitude, seasonality, and environmental controls of this noncompetitive methane production is sparse. In the present study, the presence of methanogenesis within the sulfate reduction zone (SRZ methanogenesis) was investigated in sediments (0-30 cm below seafloor, cm b.s.f.) of the seasonally hypoxic Eckernförde