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.

Chlorophyll a concentration in plankton, biomass of different taxonomic phytoplankton groups, dominating algae species, and some parameters of coastal surface waters of the Black Sea

Based on data obtained at three stations in coastal waters of the Black Sea off Sevastopol in 2000 and 2001, we present seasonal dynamics of the carbon to chlorophyll a ratio in nano- and microphy-toplankton. This parameter varied approximately tenfold throughout the year. Its maximum values (442-500) were obtained in summer (July), when Pyrrophyta dominated in phytoplankton. Minimum values (36-56) were observed in winter (December),when diatomaceous species predominated. We derive a regression relating the carbon to chlorophyll a ratio to proportion of Pyrrophyta in total phytoplankton biomass, doing so separately for warm and cold seasons. Regression equations demonstrate coupled action of irradiance, temperature, and nutrient availability on the carbon to chlorophyll a ratio. For Pyrrophyta phytoplankton assemblage R**2 = 0.95, and for diatomaceous one R**2 = 0.87.

Lead in bottom sediments, nodules, and sulfides from the Black Sea

A study of lead distribution in recent, ancient Black Sea and Neweuxinian bottom sediment shows similar vertical distributions of the element in the oxygen and hydrogen sulfide zones of the sea; i.e. hydrogen sulfide contamination does not affect lead contents in bottom sediments of the sea. Lead distribution in sediment mass of the Black Sea reflects dependence of accumulation of the element on the hydrodynamic regime of the sea and forms of its migration. It is noted that absence of lead accumulation in Black Sea nodules results from specific nodule formation and from geochemical activity of the element. A large role of diagenetic sulfide formation in lead geochemistry is shown. Degree of lead accumulation in iron sulfides depends on conditions of sedimentation and on physical and chemical parameters in the sea.

Accumulation of glucose and protein hydrolysate by natural populations of microorganisms in the Black Sea and Atlantic Ocean

Accumulation rate of dissolved organic matter (DOM) by natural populations varies over a wide range. In the surface layer of the Black Sea accumulation rate of glucose is 0.6-4.82 mg C/m**3 per day, and in the Atlantic Ocean 1.15-12.38 mg C/m**3 per day. This rate is 2-17 times higher when hydrolysate is added to the medium. Accumulation rate of glucose and hydrolysate in the aphotic layer of the Black Sea and the Atlantic Ocean is 1.5-6 times lower than at the surface. The organotrophic coefficient also varied within wide range. Relative amount of DOM used by microorganisms for growth in total production is much less (0.6-39.9%) in areas of intensive photosynthesis than in waters poor in DOM (83.7-99.2%).

Concentration of hydrogen sulfide in waters of the Black Sea in the layer of its coexistence with oxygen

About 100 parallel determinations of hydrogen sulfide by the volumetric and photometric methods were made in the layer of coexistence of oxygen with hydrogen sulfide (C layer). Thiosulfates were determined simultaneously. Regardless of locations of the stations, determinations by two methods coincided for the entire range of depths of occurrence of the C layer upper boundary. Within the C layer hydrogen sulfide readings obtained by these two independent methods agreed; thiosulfates were not found by direct measurements. Difference in the readings appears at the lower boundary of the C layer and below it, accompanied by appearance of thiosulfates. It is therefore concluded that it is correct to determine the upper boundary of the C layer by the iodometric method and to use concentration of hydrogen sulfide obtained by this method in the C layer to calculate rate of chemical oxidation of hydrogen sulfide in quasistationary processes.

Non-isoprenoidal intact polar lipids, isoprenoidal and non-isoprenoidal core lipids, isoprenoidal intact polar lipids of the Black Sea site GeoB15105 sampled during Meteor cruise M84/1 in February 2011

This PhD thesis focused on the analysis and application of microbial membrane lipids as biomarkers in marine sediments. Existing protocols for lipid extraction from marine sediments and biomass were modified. In addition, recent protocols based on high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS) as well as state-of-the-art mass spectrometric analysis by quadrupole time-of-flight (MSqTOF) and the triple quadrupole (MSQQQ) mass spectrometer were used to investigate matrix effects and evaluate the reliability of quantitative analysis in marine environmental samples. The improved lipid extraction and quantification were used to analyze Black Sea water column and sediments samples to a depth of 8 meters from site GeoB 15105 taken during cruise M84/1 (DARCSEAS) with R/V Meteor to apply lipid analysis in benthic bio systems. With this component specific differentiation between planktonic and benthic lipid signature we assessed possible lipid sources. Here, this high detail lipid fingerprinting allowed us to observe changes in the head group and lipid core structures of the intact polar lipids according to the geochemical zonation.

Age models, ostracods and trace elements of five gravity cores from the NW Black Sea

New Mg/Ca, Sr/Ca, and published stable oxygen isotope and 87Sr/86Sr data obtained on ostracods from gravity cores located on the northwestern Black Sea slope were used to infer changes in the Black Sea hydrology and water chemistry for the period between 30 to 8 ka B.P. (calibrated radiocarbon years). The period prior to 16.5 ka B.P. was characterized by stable conditions in all records until a distinct drop in d18O values combined with a sharp increase in 87Sr/86Sr occurred between 16.5 and 14.8 ka B.P. This event is attributed to an increased runoff from the northern drainage area of the Black Sea between Heinrich Event 1 and the onset of the Bølling warm period. While the Mg/Ca and Sr/Ca records remained rather unaffected by this inflow; they show an abrupt rise with the onset of the Bølling/Allerød warm period. This rise was caused by calcite precipitation in the surface water, which led to a sudden increase of the Sr/Ca and Mg/Ca ratios of the Black Sea water. The stable oxygen isotopes also start to increase around 15 ka B.P., although in a more gradual manner, due to isotopically enriched meteoric precipitation. While Sr/Ca remains constant during the following interval of the Younger Dryas cold period, a decrease in the Mg/Ca ratio implies that the intermediate water masses of the Black Sea temporarily cooled by 1-2°C during the Younger Dryas. The 87Sr/86Sr values drop after the cessation of the water inflow at 15 ka B.P. to a lower level until the Younger Dryas, where they reach values similar to those observed during the Last Glacial Maximum. This might point to a potential outflow to the Mediterranean Sea via the Sea of Marmara during this period. The inflow of Mediterranean water started around 9.3 ka B.P., which is clearly detectable in the abruptly increasing Mg/Ca, Sr/Ca, and 87Sr/86Sr values. The accompanying increase in the d18O record is less pronounced and would fit to an inflow lasting ~100 a.

(Table 1) Heat flow data in the western Black Sea

Results of heat flow measurements are presented. On the basis of new data on structure of the sedimentary sequence, corrections are introduced that take account of effect of sedimentation. Diagrammatic maps of distribution of observed and deep-seated heat flow have been constructed. A hypothesis is offered that the regional zone of anomalously high heat-flow values on the northern continental slope has been controlled by processes of subsidence of an oceanic plate beneath its continental counterpart.

Chemical composition of waters from the Black Sea

Concentrations of sulfate ions at three depths in the water column of the Black Sea were studied during cruises of the GOIN (State Oceanographic Institute) Sevastopol' Division in 1983 and 1985. Results were compared with data from earlier studies. Obtained data indicate pronounced lateral and temporal variation in the SO4/Cl ratio.

Rates of sulfide formation and oxidation in the Black Sea waters in February-April 1991

Rate of hydrogen sulfide oxidation in the redox zone of the Black Sea and rate of hydrogen sulfide formation due to bacterial sulfate reduction in the upper layer of anaerobic waters were measured in February-April 1991. These measurements were made using sulfur radioisotope under conditions close to those in situ. It was established that hydrogen sulfide is oxidized in the layer of oxygen and hydrogen sulfide coexistence under the upper boundary of the hydrogen sulfide layer. Maximum rate of hydrogen sulfide oxidation was recorded within the limits of density values dT of 16.20-16.30, while varying in the layer from 2 to 4.5 µmol/day. The average rate of hydrogen sulfide oxidation was 1.5-3 times higher than that during the warm season. Sulfide formation was not observed at most of the stations in the examined lower portion of the pycnocline layer (140 to 400 m). Noticeable sulfate reduction was detected only at one station on the northwestern shelf. Intensified hydrodynamics in the upper layers of the water mass during the cold season can be a probable reason for such noticeable changes in sulfur dynamics in the water mass of the Black Sea. Data suggesting that hydrogen sulfide oxidation proceeds under the hydrogen sulfide boundary indicate absence of the so-called "suboxic zone" in this basin.