Sulphur and iron species in Dvurechenskii mud volcano sediments

The deep Black Sea is known to be depleted in electron-acceptors for sulphide oxidation. This study on depth distributions of sulphur species (S(II), S(0),S(n)**2-,S2O3**2-,SO3**2-,SO4**2-) in the Dvurechenskii mud volcano, a cold seep situated in the permanently anoxic eastern Black Sea basin (Sorokin Trough, 2060 m water depth), showed remarkable concentrations of sulphide oxidation products. Sulphite concentrations of up to 11 µmol L**1-, thiosulphate concentrations of up to 22 µmol L**1-, zero-valent sulphur concentrations of up to 150 µmol L**1- and up to five polysulphide species were measured in the upper 20 cm of the sediment. Electron-acceptors found to be available in the Dvurechenskii mud volcano (DMV) for the oxidation of hydrogen sulphide to sulphide oxidation intermediates are iron-minerals, and probably also reactive manganese phases. Up to 60 µmol g**1- of reactive iron-minerals and up to 170 µmol L**1- dissolved iron was present in the central summit with the highest fluid upflow and fresh mud outflow. Thus, the source for the oxidative power in the DMV are reactive iron phases extruded with the mud from an ancient source in the deeply buried sediments, leading to the formation of various sulphur intermediates in comparably high concentrations. Another possible source of sulphide oxidation intermediates in DMV sediments could be the formation of zero-valent sulphur by sulphate dependent anaerobic microbial oxidation of methane followed by disproportionation of zero-valent sulphur. Sulphide oxidation intermediates, which are produced by these processes, do not reach thermodynamic equilibrium with rhombic sulphur, especially close to the active center of the DMV due to a short equilibration time. Thus, mud volcano sediments, such as in the DMV, can provide oxidizing niches even in a highly reduced environment like the abyssal part of the Black Sea.

Chemical composition of bottom waters and interstitial waters from sediments and deposits within and outside the Haakon Mosby submarine mud volcano in the Norwegian Sea

On the base of data of Cruise 40 of R/V Akademik Keldysh features of formation of saline composition of interstitial waters from sediments containing free hydrocarbons (methane) and gas hydrates (CH4 x 6H2O) were considered. Chemical composition of the interstitial waters is presented for three zones of sediments from the Haakon Mosby submarine mud volcano: (1) zone of kettles containing free hydrocarbons, (2) gas hydrate sediments, and (3) periphery of the volcano. Abnormally high concentrations of bromine and especially iodine characteristic of the interstitial and particularly of the oil-field waters were found. Because of a great interest in natural gas hydrates found in marine sediments, we obtained a possibility to supplement scarce of available published data with some new information.

Eruption of the Håkon Mosby mud volcano recorded by the long-term observatory on mud-volcano eruptions (LOOME) between 2009 and 2010

Submarine mud volcanoes are considered an important source of methane to the water column. However, the temporal variability of their fluid transport including mud and methane emissions is largely unknown. Assuming that this transport was continuous and at steady state, methane emissions were previously proposed to result from a dynamic equilibrium between upward migration and consumption at the seabed by methane-consuming microbes. Here we have investigated non-steady state situations of vigorous mud movements and their reflection in fluid flow, seabed temperature and bathymetry. Time series of pressure, temperature, pH and seafloor photography were collected by a benthic observatory (LOOME) for 431 days at the active Håkon Mosby mud volcano. These new data document eruptions, which were accompanied by pulses of hot subsurface fluids and triggered rapid sediment uplift and lateral movement, as well as emissions of free gas.

Terrain model of the Håkon Mosby Mud Volcano (10 m grid size)

The Håkon Mosby Mud Volcano is a natural laboratory to study geological, geochemical, and ecological processes related to deep-water mud volcanism. High resolution bathymetry of the Håkon Mosby Mud Volcano was recorded during RV Polarstern expedition ARK-XIX/3 utilizing the multibeam system Hydrosweep DS-2. Dense spacing of the survey lines and slow ship speed (5 knots) provided necessary point density to generate a regular 10 m grid. Generalization was applied to preserve and represent morphological structures appropriately. Contour lines were derived showing detailed topography at the centre of the Håkon Mosby Mud Volcano and generalized contours in the vicinity. We provide a brief introduction to the Håkon Mosby Mud Volcano area and describe in detail data recording and processing methods, as well as the morphology of the area. Accuracy assessment was made to evaluate the reliability of a 10 m resolution terrain model. Multibeam sidescan data were recorded along with depth measurements and show reflectivity variations from light grey values at the centre of the Håkon Mosby Mud Volcano to dark grey values (less reflective) at the surrounding moat.

Autonomous recording current meter measurements at the Håkon Mosby mud volcano (LOOME)

The deployment of LOOME was performed by lowering the LOOME frame by winch, followed by positioning of the surface sensors across the most active site by ROV. The frame was placed on an inactive slab of hydrates, eastwards and adjacent to the hot spot. To the frame autonomous recording current meter was mounted, recording physical oceanography variables approximately two to three meter above the seafloor.

Methane and sulfide fluxes in permanent anoxia: in situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV), located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea), was visited during the M72/2 cruise with the RV Meteor to investigate the methane and sulfide release from mud volcanoes into the Black Sea hydrosphere. We studied benthic fluxes of methane and sulfide, and the factors controlling transport, consumption and production of both compounds within the sediment. The pie shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at a small elevation north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was excluded from this zone due to fluid-flow induced sulfate limitation and a fresh mud flow and consequently methane escaped into the water column with a rate of 0.46 mol/m**2/d. In the outer center of the mud volcano fluid flow and total methane flux were decreased, correlating with an increase in sulfate penetration into the sediment, and with higher SR and AOM rates. Here between 50-70% of the methane flux (0.07-0.1 mol/m**2/d) was consumed within the upper 10 cm of the sediment. Also at the edge of the mud volcano fluid flow and rates of methane and sulfate turnover were substantial. The overall amount of dissolved methane released from the mud volcano into the water column was significant with a discharge of 1.4x10**7 mol/yr. The DMV maintains also high areal rates of methane-fueled sulfide production of on average 0.05 mol/m**2/d. However, we concluded that sulfide and methane emission into the hydrosphere from deep water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.

Methane discharge in sediments of the Dvurechenskii mud volcano

During the MARGASCH cruise M52/1 in 2001 with RV Meteor we sampled surface sediments from three stations in the crater of the Dvurechenskii mud volcano (DMV, located in the Sorokin Trough of the Black Sea) and one reference station situated 15 km to the northeast of the DMV. We analysed the pore water for sulphide, methane, alkalinity, sulphate, and chloride concentrations and determined the concentrations of particulate organic carbon, carbonate and sulphur in surface sediments. Rates of anaerobic oxidation of methane (AOM) were determined using a radiotracer (14CH4) incubation method. Numerical transport-reaction models were applied to derive the velocity of upward fluid flow through the quiescently dewatering DMV, to calculate rates of AOM in surface sediments, and to determine methane fluxes into the overlying water column. According to the model, AOM consumes 79% of the average methane flux from depth (8.9 x 10**+ 6 mol a**-1), such that the resulting dissolved methane emission from the volcano into the overlying bottom water can be determined as 1.9 x 10**+ 6 mol a**-1. If it is assumed that all submarine mud volcanoes (SMVs) in the Black Sea are at an activity level like the DMV, the resulting seepage represents less than 0.1% of the total methane flux into this anoxic marginal sea. The new data from the DMV and previously published studies indicate that an average SMV emits about 2.0 x 10**+ 6 mol a**-1 into the ocean via quiescent dewatering. The global flux of dissolved methane from SMVs into the ocean is estimated to fall into the order of 10**+10 mol a**-1. Additional methane fluxes arise during periods of active mud expulsion and gas bubbling occurring episodically at the DMV and other SMVs.

Meiobenthos at the Arctic Håkon Mosby Mud Volcano

Håkon Mosby Mud Volcano (HMMV, SW Barents Sea slope, 1280 m) is one of the numerous cold methane-venting seeps existing along the continental margins. Analyses of video-guided core samples revealed extreme differences in the diversity and density of the metazoan meiobenthic communities associated with the different sub-habitats (centre, microbial mats, Pogonophora field, outer rim) of this mud volcano. Diversity was lowest in the sulphidic, microbial mat sediments that supported the highest standing stock, with unusually high densities (11000 ind./10 cm**2) of 1 nematode species related to Geomonhystera disjuncta. Stable carbon isotope analyses revealed that this nematode species was thriving on chemosynthetically derived food sources in these sediments. Ovoviviparous reproduction has been identified as an important adaptation of parents securing the survival and development of their brood in this toxic environment. The proliferation of this single species in exclusive association with free-living, sulphide-oxidising bacteria (Beggiatoa) indicates that its dominance is strongly related to trophic specialisation, evidently uncommon among the meiofauna. This chemoautotrophic association was replaced by copepods in the bare, sulphide-free sediments of the volcano's centre, dominated by aerobic methane oxidation as the chemosynthetic process. Copepods and nauplii reached maximum densities and dominance in the volcano's centre (500 ind./10 cm**2). Their strongly depleted carbon isotope signatures indicated a trophic link with methane-derived carbon. This proliferation of only selected meiobenthic species supported by chemosynthetically derived carbon suggests that, in addition to the sediment geochemistry, the associated reduced meiobenthic diversity may equally be related to the trophic resource specificity in HMMV sub-habitats.