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Abstract: 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 (8.9·10+6 mol a−1), such that the resulting dissolved methane emission from the volcano into the overlying bottom water can be determined as 1.9·10+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 2.0·10+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. [Copyright &y& Elsevier] more...

Significant sediment–ocean chemical fluxes are produced by the expulsion of sedimentary fluids at continental margins. Although such fluxes could play a role in global geochemical cycles, few quantitative estimates of their global, or even regional, significance exist. We carried out a pore water geochemical study of fluids expelled from the Dvurechenskii mud volcano (DMV) in the Black Sea, with the aim of understanding the role played by mud volcanoes in Black Sea geochemical cycles. The DMV is presently expelling highly saline fluids particularly enriched in geochemically important species such as Li+ (1.5 mM), B (2.17 mM), Ba2+ (0.57 mM), Sr2+ (0.79 mM), I (0.4 mM) and dissolved inorganic nitrogen (DIN) (22 mM). A combination of geochemical indicators shows that this geochemical signature was acquired via organic matter and silicate alteration processes in the subsurface down to 3-km depth and near-surface gas hydrate formation. We used a simple transport model to estimate the benthic fluxes of these solutes at the DMV. Our results show that the DMV is expelling fluids at a rather low seepage rate (8–25 cm year−1) resulting in a total water flux of 9.4×10−5 km3 year−1. This gentle regime of fluid expulsion results in Li+, B, Sr2+, I and DIN fluxes between 3.8×104 and 2.1×106 mol year−1. Surface biogeochemical processes affect the benthic fluxes of Ba2+ such that the deep Ba2+ flux is completely consumed through the precipitation of authigenic barite (BaSO4) in surface sediments. The Black Sea I cycle is likely to be affected by mud volcanism, if the 50 known Black Sea mud volcanoes share the rather sluggish activity of the DMV. Mud volcano fluxes of Li, B, Sr and DIN, instead, are too small to affect Black Sea geochemical cycles. On a global scale, mud volcanism could play a role in the marine cycles of Li, B, Sr, I and DIN if current estimates of mud volcano abundance are correct. [Copyright &y& Elsevier] more...

Abstract: Four seep sites located within an ∼20km2 area offshore Georgia (Batumi seep area, Pechori Mound, Iberia Mound, and Colkheti Seep) show characteristic differences with respect to element concentrations, and oxygen, hydrogen, strontium, and chlorine isotope signatures in pore waters, as well as impregnation of sediments with petroleum and hydrocarbon potential. All seep sites have active gas seepage, near surface authigenic carbonates and gas hydrates. Cokheti Seep, Iberia Mound, and Pechori Mound are characterized by oil-stained sediments and gas seepage decoupled from deep fluid advection and bottom water intrusion induced by gas bubble release. Pechori Mound is further characterized by deep fluid advection of lower salinity pore fluids. The Pechori Mound pore fluids are altered by mineral/water reactions at elevated temperatures (between 60 and 110°C) indicated by heavier oxygen and lighter chlorine isotope values, distinct Li and B enrichment, and K depletion. Strontium isotope ratios indicate that fluids originate from late Oligocene strata. This finding is supported by the occurrence of hydrocarbon impregnations within the sediments. Furthermore, light hydrocarbons and high molecular weight impregnates indicate a predominant thermogenic origin for the gas and oil at Pechori Mound, Iberia Mound, and Colkheti Seep. C15+ hydrocarbons at the oil seeps are allochtonous, whereas those at the Batumi seep area are autochthonous. The presence of oleanane, an angiosperm biomarker, suggests that the hydrocarbon source rocks belong to the Maikopian Formation. In summary, all investigated seep sites show a high hydrocarbon potential and hydrocarbons of Iberia Mound, Colkheti Seep, and Pechori Mound are predominantly of thermogenic origin. However, only at the latter seep site advection of deep pore fluids is indicated. [Copyright &y& Elsevier] more...

Abstract: Vodyanitskii mud volcano is located at a depth of about 2070m in the Sorokin Trough, Black sea. It is a 500-m wide and 20-m high cone surrounded by a depression, which is typical of many mud volcanoes in the Black Sea. 75kHz sidescan sonar show different generations of mud flows that include mud breccia, authigenic carbonates, and gas hydrates that were sampled by gravity coring. The fluids that flow through or erupt with the mud are enriched in chloride (up to ∼650mmolL−1 at ∼150-cm sediment depth) suggesting a deep source, which is similar to the fluids of the close-by Dvurechenskii mud volcano. Direct observation with the remotely operated vehicle Quest revealed gas bubbles emanating at two distinct sites at the crest of the mud volcano, which confirms earlier observations of bubble-induced hydroacoustic anomalies in echosounder records. The sediments at the main bubble emission site show a thermal anomaly with temperatures at ∼60cm sediment depth that were 0.9°C warmer than the bottom water. Chemical and isotopic analyses of the emanated gas revealed that it consisted primarily of methane (99.8%) and was of microbial origin (δD-CH4 =−170.8‰ (SMOW), δ 13C-CH4 =−61.0‰ (V-PDB), δ 13C-C2H6 =−44.0‰ (V-PDB)). The gas flux was estimated using the video observations of the ROV. Assuming that the flux is constant with time, about 0.9±0.5×106 mol of methane is released every year. This value is of the same order-of-magnitude as reported fluxes of dissolved methane released with pore water at other mud volcanoes. This suggests that bubble emanation is a significant pathway transporting methane from the sediments into the water column. [Copyright &y& Elsevier] more...