Methane concentration in sediment cores during METEOR cruise M92

We studied the concurrence of methanogenesis and sulfate reduction in surface sediments (0-25 cm below sea floor, cmbsf) at six stations (70, 145, 253, 407, 770 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 cmbsf of multicorer cores from all stations, while deep hydrogenotrophic methanogenesis (> 30 cmbsf, 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 cmbsf, 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 decline 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 of methanogenesis rates with 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 indicate a partial release of surface methane into the water column as well as a partial 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.

Methane measurements during POLARSTERN cruise ARK-XXII/2

A methane surplus relative to the atmospheric equilibrium is a frequently observed feature of ocean surface water. Despite the common fact that biological processes are responsible for its origin, the formation of methane in aerobic surface water is still poorly understood. We report on methane production in the central Arctic Ocean, which was exclusively detected in Pacific derived water but not nearby in Atlantic derived water. The two water masses are distinguished by their different nitrate to phosphate ratios. We show that methane production occurs if nitrate is depleted but phosphate is available as a P source. Apparently the low N:P ratio enhances the ability of bacteria to compete for phosphate while the phytoplankton metabolite dimethylsulfoniopropionate (DMSP) is utilized as a C source. This was verified by experimentally induced methane production in DMSP spiked Arctic sea water. Accordingly we propose that methylated compounds may serve as precursors for methane and thermodynamic calculations show that methylotrophic methanogenesis can provide energy in aerobic environments.

Field data on methane fluxes, temperature, soil gas profiles and microbial activities in ponds of the northeast Siberian polygonal tundra

The data files give the basic field and laboratory data on five ponds in the northeast Siberian Arctic tundra on Samoylov. The files contain water and soil temperature data of the ponds, methane fluxes, measured with closed chambers in the centres without vascular plants and the margins with vascular plants, the contribution of plant mediated fluxes on total methane fluxes, the gas concentrations (methane and dissolved inorganic carbon, oxygen) in the soil and the water column of the ponds, microbial activities (methane production, methane oxidation, aerobic and anaerobic carbon dioxide production), total carbon pools in the different horizons of the bottom soils, soil bulk density, soil substance density, and soil porosity.

Sedimentation rate calculations and isotopic analysis on sediment cores along the IODP Expedition 311 transect

The oceanographic and tectonic conditions of accretionary margins are well-suited for several potential processes governing methane generation, storage and release. To identify the relevant methane evolution pathways in the northern Cascadia accretionary margin, a four-site transect was drilled during Integrated Ocean Drilling Program Expedition 311. The d13C values of methane range from a minimum value of -82.2 per mil on an uplifted ridge of accreted sediment near the deformation front (Site U1326, 1829 mbsl, meters below sea level) to a maximum value of -39.5 per mil at the most landward location within an area of steep canyons near the shelf edge (Site U1329, 946 mbsl). An interpretation based solely on methane isotope values might conclude the 13C-enrichment of methane indicates a transition from microbially- to thermogenically-sourced methane. However, the co-existing CO2 exhibits a similar trend of 13C-enrichment along the transect with values ranging from -22.5 per mil to +25.7 per mil. The magnitude of the carbon isotope separation between methane and CO2 (Ec = 63.8 ± 5.8) is consistent with isotope fractionation during microbially mediated carbonate reduction. These results, in conjunction with a transect-wide gaseous hydrocarbon content composed of > 99.8% (by volume) methane and uniform dDCH4 values (-172 per mil ± 8) that are distinct from thermogenic methane at a seep located 60 km from the Expedition 311 transect, suggest microbial CO2 reduction is the predominant methane source at all investigated sites. The magnitude of the intra-site downhole 13C-enrichment of CO2 within the accreted ridge (Site U1326) and a slope basin nearest the deformation front (Site U1325, 2195 mbsl) is ~ 5 per mil. At the mid-slope site (Site U1327, 1304 mbsl) the downhole 13C-enrichment of the CO2 is ~ 25 per mil and increases to ~ 40 per mil at the near-shelf edge Site U1329. This isotope fractionation pattern is indicative of more extensive diagenetic alteration at sites with greater 13C-enrichment. The magnitude of the 13C-enrichment of CO2 correlates with decreasing sedimentation rates and a diminishing occurrence of stratigraphic gas hydrate. We suggest the decreasing sedimentation rates increase the exposure time of sedimentary organic matter to aerobic and anaerobic degradation, during burial, thereby reducing the availability of metabolizable organic matter available for methane production. This process is reflected in the occurrence and distribution of gas hydrate within the northern Cascadia margin accretionary prism. Our observations are relevant for evaluating methane production and the occurrence of stratigraphic gas hydrate within other convergent margins.

Petrography, minerals and isotopic composition at DSDP Leg 66 Holes

We collected 20 carbonate nodules from the inner trench slope deposits of the Middle America Trench area off Mexico. Carbonate nodules are found only within the methane-rich layer beneath the mixed layer of methane and hydrogen sulfide. They have been investigated by microscopic, scanning electron microscopic (SEM), X-ray diffraction, and stable isotopic analytical methods. Calcite, magnesian calcite, dolomite, and rhodochrosite were recognized as carbonate minerals. Each carbonate nodule is usually represented by single species of carbonate minerals. Carbonate nodules are subdivided into micrite nodules and recrystallized nodules according to textural features. The carbonate crystallites in each micrite nodule are equidimensional. Their sizes range from several to 30 µm, as revealed by SEM micrographs. The chemical composition of calcite is changed from pure calcite to high magnesian calcite, as shown by the shift of the (104) reflection in X-ray diffraction patterns. Fe substitution for Ca in dolomite was also observed. Carbon isotopic composition shows an unusually wide range - from -42.9 to +13.5 per mil - in PDB scale, whereas oxygen isotopic compositions of almost all the carbonate nodules are constantly enriched in 18O from +3.4 to +7.60 per mil in PDB scale. These wide variations in carbon isotopic composition indicate several sources for the carbon in carbonate nodules. Carbon with a negative d13C value was derived from biochemical oxidation of methane with a negative d13C value. On the other hand, carbon with positive d13C value was probably formed during methane production in an anoxic condition.

Chemistry of interstitial waters and sediments at DSDP Leg 64 Holes

Studies of interstitial waters obtained from DSDP Leg 64 drill sites in the Gulf of California have revealed information both on early diagenetic processes in the sediments resulting from the breakdown of organic matter and on hydrothermal interactions between sediments and hot doleritic sill intrusions into the sediments. In all the sites drilled sulfate reduction occurred as a result of rapid sediment accumulation rates and of relatively high organic carbon contents; in most sites methane production occurred after sulfate depletion. Associated with this methane production are high values of alkalinity and high concentrations of dissolved ammonia, which causes ion exchange processes with the solid phases leading to intermediate maxima in Mg++, K+, Rb+, and Sr++(?). Though this phenomenon is common in Leg 64 drill sites, these concentration reversals had been noticed previously only in Site 262 (Timor Trough) and Site 440 (Japan Trench). Penetrating, hot dolerite sills have led to substantial hydrothermal alteration in sediments at sites drilled in the Guaymas Basin. Site 477 is an active hydrothermal system in which the pore-water chemistry typically shows depletions in sulfate and magnesium and large increases in lithium, potassium, rubidium, calcium, strontium, and chloride. Strontium isotope data also indicate large contributions of volcanic matter and basalt to the pore-water strontium concentrations. At Sites 478 and 481 dolerite sill intrusions have cooled to ambient temperatures but interstitial water concentrations of Li+, Rb+, Sr++ , and Cl- show the gradual decay of a hydrothermal signal that must have been similar to the interstitial water chemistry at Site 477 at the time of sill intrusion. Studies of oxygen isotopes of the interstitial waters at Site 481 indicate positive values of d18O (SMOW) as a result of high-temperature alteration reactions occurring in the sills and the surrounding sediments. A minimum in dissolved chloride at about 100-125 meters sub-bottom at Sites 478, 481, and particularly Site 479 records a possible paleosalinity signal, associated with an event that substantially lowered salinities in the inner parts of the Gulf of California during Quaternary time.

Biogeochemistry (speciation and isotopes of S and C) in bottom sediments, water and bacterial mats from the White Sea

This publication presents results of microbiological and biogeochemical studies in the White Sea. Material was obtained during a series of expeditions in 1999-2002. The studies were carried out in the open part of the White Sea, in the Onega, Dvina and Kandalaksha Bays, as well as in the intertidal zone of the Kandalaksha Bay. Quantitative characteristics of activity of microbial processes in waters and bottom sediments of the White Sea were obtained. The total number of bacteria was equal to 150000-800000 cells/ml, and intensity of dark CO2 assimilation was equal to 0.9-17 µg C/l/day. Bacterial sulfate reduction was equal to 3-150 mg S/m**2/day, and methane formation and oxidation was equal to 13-6840 and 20-14650 µl CH4/m**2/day, respectively. Extremely high values of intensity of all principal microbial processes were found in intertidal sediments rich in organic matter: under decomposing macrophytes, in local pits at the lower intertidal boundary, and in the mouth of a freshwater brook. Average hydrogen sulfide production in highly productive intertidal sediments was 1950-4300 mg S/m**2/day, methane production was 0.5-8.7 ml CH4/m**2/day, and intensity of methane oxidation was up to 17.5 ml CH4/m**2/day. Calculations performed with account for areas occupied by microlandscapes of increased productivity showed that diurnal production of H2S and CH4 per 1 km**2 of the intertidal zone (August) was estimated as 60.8-202 kg S/km**2/day and 192-300 l CH4/km**2/day, respectively.

Carbon and deuterium isotopes and C ratios in gas hydrates of ODP Leg 204 sites

Sediments at the southern summit of Hydrate Ridge display two distinct modes of gas hydrate occurrence. The dominant mode is associated with active venting of gas exsolved from the accretionary prism and leads to high concentrations (15%-40% of pore space) of gas hydrate in seafloor or near-surface sediments at and around the topographic summit of southern Hydrate Ridge. These near-surface gas hydrates are mainly composed of previously buried microbial methane but also contain a significant (10%-15%) component of thermogenic hydrocarbons and are overprinted with microbial methane currently being generated in shallow sediments. Focused migration pathways with high gas saturation (>65%) abutting the base of gas hydrate stability create phase equilibrium conditions that permit the flow of a gas phase through the gas hydrate stability zone. Gas seepage at the summit supports rapid growth of gas hydrates and vigorous anaerobic methane oxidation. The other mode of gas hydrate occurs in slope basins and on the saddle north of the southern summit and consists of lower average concentrations (0.5%-5%) at greater depths (30-200 meters below seafloor [mbsf]) resulting from the buildup of in situ-generated dissolved microbial methane that reaches saturation levels with respect to gas hydrate stability at 30-50 mbsf. Net rates of sulfate reduction in the slope basin and ridge saddle sites estimated from curve fitting of concentration gradients are 2-4 mmol/m**3/yr, and integrated net rates are 20-50 mmol/m**2/yr. Modeled microbial methane production rates are initially 1.5 mmol/m**3/yr in sediments just beneath the sulfate reduction zone but rapidly decrease to rates of <0.1 mmol/m**3/yr at depths >100 mbsf. Integrated net rates of methane production in sediments away from the southern summit of Hydrate Ridge are 25-80 mmol/m**2/yr. Anaerobic methane oxidation is minor or absent in cored sediments away from the summit of southern Hydrate Ridge. Ethane-enriched Structure I gas hydrate solids are buried more rapidly than ethane-depleted dissolved gas in the pore water because of advection from compaction. With subsidence beneath the gas hydrate stability zone, the ethane (mainly of low-temperature thermogenic origin) is released back to the dissolved gas-free gas phases and produces a discontinuous decrease in the C1/C2 vs. depth trend. These ethane fractionation effects may be useful to recognize and estimate levels of gas hydrate occurrence in marine sediments.