Long-period variability of oxygen dissolved in Black Sea waters

Doklady Earth Sciences - Using an archival database from the Institute of Natural and Technical Systems, the low-frequency variability of oxygen dissolved in the deep-water and northwestern parts...     

Formation of iron sulfide nodules during anaerobic oxidation of methane

The biomarker compositions of iron sulfide nodules (ISNs; upper Pliocene Valle Ricca section near Rome, Italy) that contain the ferrimagnetic mineral greigite (Fe₃S₄) were examined. In addition to the presence of specific terrestrial and marine biomarkers, consistent with formation in coastal marine sediments, these ISNs contain compounds thought to originate from sulfate reducing bacteria (SRB). These compounds include a variety of low-molecular-weight and branched alkanols and several non-isoprenoidal dialkyl glycerol diethers (DGDs). In addition, archaeal biomarkers, including archaeol, macrocyclic isoprenoidal DGDs and isoprenoidal glycerol dialkyl glycerol tetraethers are also present. Both SRB and archaeal lipid δ¹³C values are depleted in ¹³C (δ¹³C values are typically less than −50‰), which suggests that the SRB and archaea consumed ¹³C depleted methane. These biomarker and isotopic signatures are similar to those found in cold seeps and marine sediments where anaerobic oxidation of methane (AOM) occurs with sulfate serving as the terminal electron acceptor. Association of AOM with formation of greigite-containing ISNs could provide an explanation for documented remagnetization of the Valle Ricca sediments. Upward migration of methane, subsequent AOM and associated authigenic greigite formation are widespread processes in the geological record that have considerable potential to compromise paleomagnetic records.     

Stenols and stanols in the oxic and anoxic waters of the Black Sea

Water samples collected from a slope station and two deep stations in the western basin of the Black Sea were analyzed for stenols and stanols by glass capillary gas chromatography. These results were used in conjuction with hydrographic, particulate organic carbon, and chlorophyll a data to better understand sterol sources and their transport and transformation mechanisms in anoxic basins.The total free sterol concentrations found in the surface waters were 450–500 ng/l dropping rapidly to values well below 100 ng/l at depths below the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. In the upper 200 m of the water column a strong association of sterols with particulate matter is suggested. Structural elucidation by a gas chromatograph-mass spectrometer-computer system revealed the presence of at least sixteen different stenols and stanols in the surface waters of the Black Sea. Cholesterol, 24-methylenecholesterol and 24-methylcholesta-5,22-dien-3β-ol were the major sterols in the surface waters. Cholesterol and 24-ethylcholesterol both exhibited a subsurface maximum at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. In the anoxic deep waters (200–2000 m) only cholesterol and 24-ethylcholesterol were found. Two stenols were found that have not been reported in seawater: a C₂₆ stenol with a saturated C₇H₁₅ side chain (presumably 24-norcholesterol) and 24-ketocholesterol. At least six 5α-stanols could be identified in the surface samples, each of them comprising about 10–20% of the concentration of the corresponding Δ5-stenol. From these comparatively high surface values the stanol concentrations drop rapidly to values near zero at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface. Except for very low concentrations of 5α-cholestanol (< 4ng/l) no other stanols could be detected in the anoxic zone.From this data it appears that no detectable stenol → stanol conversion is occurring at the $\text{O}{}_2\text{H}{}_2\text{S}$ interface or in the deep anoxic waters of the Black Sea.     

Thermodynamic and kinetic control on anaerobic oxidation of methane in marine sediments

The free energy yield of microbial respiration reactions in anaerobic marine sediments must be sufficient to be conserved as biologically usable energy in the form of ATP. Anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SRR) has a very low standard free energy yield of ΔG^° = −33 kJ mol⁻¹, but the in situ energy yield strongly depends on the concentrations of substrates and products in the pore water of the sediment. In this work ΔG for the AOM-SRR process was calculated from the pore water concentrations of methane, sulfate, sulfide, and dissolved inorganic carbon (DIC) in sediment cores from different sites of the European continental margin in order to determine the influence of thermodynamic regulation on the activity and distribution of microorganisms mediating AOM-SRR. In the zone of methane and sulfate coexistence, the methane-sulfate transition zone (SMTZ), the energy yield was rarely less than −20 kJ mol⁻¹ and was mostly rather constant throughout this zone. The kinetic drive was highest at the lower part of the SMTZ, matching the occurrence of maximum AOM rates. The results show that the location of maximum AOM rates is determined by a combination of thermodynamic and kinetic drive, whereas the rate activity mainly depends on kinetic regulation.     

Morphology and formation mechanism of pyrite induced by the anaerobic oxidation of methane from the continental slope of the NE South China Sea

In order to understand the response of authigenic pyrite to gas hydrate geo-systems, pyrite tubes or rods at the sulfate–methane transition (SMT) zone of core GC10 from the northern continental slope of the South China Sea (SCS) were investigated. In situ X-ray diffraction (XRD) results show that the pyrite tube consists of pyrite micro-crystals with trace amount of graphite in the inner tube. Scanning electron microscope (SEM) observations of pyrite tubes indicate various aggregations in the form of framboidal, euhedral, and colloidal pyrite microcrystals. Typical framboidal pyrite is considered as packing of octahedral microcrystals. Interestingly, many framboids in the tubes consist of round or irregular microcrystals and have an outer crust that consists of secondary pyrite. The size of the framboids in the inner wall of the tube is larger than that in the middle wall or foraminifer-filled pyrite. High-resolution transmission electron microscopic (HRTEM) images show marcasite lamellae defects in the spherulitic pyrite crystals, which reveal different solution conditions during the pyrite precipitation. Nano-foil-like graphitic carbon was observed to be closely associated with the pyrite spherules. The occurrence of both marcasite layers and nano-foil-like graphitic carbon suggest that the migration of methane from deep sediment. It is suggested that the formation of pyrite serves as a catalyst during the reaction from methane to elemental carbon under the anaerobic oxidation of methane. Meanwhile, this reaction results in local acidification of the solution inside the pyrite tubes, which favors marcasite lamellae growth on the host pyrite substrate.     

Detection of methane ebullition in shelf waters of the Laptev Sea in the Eastern Arctic Region

Doklady Earth Sciences -     

Anaerobic methane oxidation and a deep H2S sink generate isotopically heavy sulfides in Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO₄²⁻-CH₄ transition where H₂S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H₂S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe²⁺ diffusing up from below. The H₂S-Fe²⁺ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO₄²⁻ and 10 yr for H₂S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO₄²⁻-CH₄ and H₂S-Fe²⁺ cause the trapping of isotopically heavy iron sulfide with δ³⁴S = +15 to +33‰ at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO₄²⁻ diffusing downward into the SO₄²⁻-CH₄ transition has an isotopic composition of +19‰, close to the +23‰ of H₂S diffusing upward. These isotopic compositions are, however, very different from the porewater SO₄²⁻ (+43‰) and H₂S (−15‰) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H₂S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth’s history.     

Influence of the economic activities on coasts upon the coastal waters of the Black Sea

The contemporary state of the ecosystem, coastal waters and coasts of the Black Sea can be assessed as critical. The main causes of unfavourable ecological changes of the sea, and especially its shelf waters, are the natural and anthropogenic changes in river runoff increase of biogenic compounds, organic matter, pollutants and toxic agents carried to the sea in river waters, pollution of the sea water basin with petroleum. This work is devoted to an assessment of the role of sea coasts in the change of its ecological state because up till now the majority of researchers considered the influence of quantitative and qualitative changes of the river runoff produced by the economic activities to be decisive. It is shown that even according to at present incomplete data the contribution of coasts of biogenic compounds to the coastal sea waters is comparable with the contribution of the runoff of large rivers; it is significant for oil hydrocarbons, and decisive with regard to surface acting agents (SAA), phenols and pesticides. In a number of areas the ecological state of the coastal waters is almost completely determined by the inflow of pollutants from coasts. The integral assessment of the quality of coastal sea waters on different areas of the sea proved that the quality of the water along the coasts of Georgia, Russia and the Ukraine varies from moderately polluted to extremely dirty.     

Mud volcanoes of the Black Sea as a prospecting indicator of methane gas hydrates

Relationship between methane gas hydrates and mud volcanoes in the Black Sea is considered. It is suggested that they are mainly confined to compensation troughs near mud volcanoes.     

Composition of interstitial waters and forms of sulfur compounds in bottom sediments in the northeastern Black Sea

Study of sediments and water column in the Black Sea has been carried out for a long time. However, issues of the formation of seawater and sediments in the geological (ancient) and Recent marine history remain debatable so far. Studies of the physical, biological, and biogeochemical settings in the northeastern part of the Black Sea carried out onboard the R/V Professor Shtokman in 2009 yielded new data on this region. The present paper reports the results of study of the chemical composition of bottom sediments and interstitial waters from the meridional profile extending from the Kerch Peninsula to the central part of the eastern deep-water depression.     

Separating contributions from natural and anthropogenic sources in atmospheric methane from the Black Sea region,Romania

The Danube Delta-Black Sea region of Romania is an important wetland, and this preliminary study evaluates the significance of this region as a source of atmospheric CH₄. Measurements of the mixing ratio and δ¹³C in CH₄ are reported from air and water samples collected at eight sites in the Danube Delta. High mixing ratios of CH₄ were found in air (2500–14,000 ppb) and dissolved in water samples (∼1–10 μmol L⁻¹), demonstrating that the Danube Delta is an important natural source of CH₄. The intercepts on Keeling plots of about −62‰ show that the main source of CH₄ in this region is microbial, probably resulting primarily from acetate fermentation. Atmospheric CH₄ and CO data from the NOAA/ESRL (National Oceanic and Atmospheric Administration/Earth System Research Laboratory) were used to make a preliminary estimate of biogenic CH₄ at the Black Sea sampling site at Constanta (BSC). These data were used to calculate ratios of CH₄/CO in air samples, and using an assumed CH₄/CO anthropogenic emissions ratio of 0.6, fossil fuel emissions at BSC were estimated. Biogenic CH₄ emissions were then estimated by a simple mass balance approach. Keeling plots of well-mixed air from the BSC site suggested a stronger wetland source in summer and a stronger fossil fuel source in winter.     

Manganese(II) oxidation driven by lateral oxygen intrusions in the western Black Sea

Mn(II) oxidation in the suboxic zone of the water column was studied at four stations in the western Black Sea. We measured Mn(II) oxidation rates using ⁵⁴Mn tracer and tested the hypothesis of alternative oxidants for Mn(II) other than dissolved oxygen. In anoxic incubation experiments with water from different depths of the chemocline, Mn(II) was not oxidized by nitrite, nitrate, or iodate. In the presence of light, Mn(II) also was not oxidized under anoxic conditions as well. Anaerobic Mn(II) oxidizing microorganisms could not be enriched. In oxic incubation experiments, the addition of alternative oxidants did not significantly increase the Mn(II) oxidation rate. The lack of an anaerobic Mn(II) oxidation in our experiments does not unambiguously prove the absence of anaerobic Mn(II) oxidation in the Black Sea but suggests that dissolved oxygen is the only oxidant for biologically catalyzed Mn(II) oxidation. Lateral intrusions of modified Bosphorus water were shown to be the main mechanism providing dissolved oxygen in the suboxic and the upper anoxic zones and explaining observed Mn(II) oxidation rates. Maximum in situ Mn(II) oxidation rates in the suboxic zone were 1.1 nM Mn(II) per h in the central Black Sea, 25 nM Mn(II) per h on the Romanian continental slope and 60 nM Mn(II) per h on the Anatolian continental slope. These rates correlate with the amount of particulate Mn and the number of Mn-oxide particles and are in agreement with rates measured 13 yr before. Our study highlights the importance of lateral intrusions of oxygen for the ventilation of the suboxic zone and the anoxic interior and for the regulation of different oxidation-reduction processes in the chemocline, including Mn(II) oxidation, which may be significant for other anoxic basins as well.     

Messinian events in the Black Sea

Past hydrological interactions between the Mediterranean Sea and Black Sea are poorly resolved due to complications in establishing a high‐resolution time frame for the Black Sea. We present a new greigite‐based magnetostratigraphic age model for the Mio‐Pliocene deposits of DSDP Hole 380/380A, drilled in the southwestern Black Sea. This age model is complemented by ⁴⁰Ar/³⁹Ar dating of a volcanic ash layer, allowing a direct correlation of Black Sea deposits to the Messinian salinity crisis (MSC) interval of the Mediterranean Sea. Proxy records divide these DSDP deposits into four intervals: (i) Pre‐MSC marine conditions (6.1–6.0 Ma); (ii) highstand, fresh to brackish water conditions (~6.0–5.6 Ma); (iii) lowstand, fresh‐water environment (5.6–5.4 Ma) and (iv) highstand, fresh‐water conditions (5.4–post 5.0 Ma). Our results indicate the Black Sea was a major fresh‐water source during gypsum precipitation in the Mediterranean Sea. The introduction of Lago Mare fauna during the final stage of the MSC coincides with a sea‐level rise in the Black Sea. Across the Mio‐Pliocene boundary, sea‐level and salinity in the Black Sea did not change significantly.     

Molecular biogeochemistry of sulfate reduction, methanogenesis and the anaerobic oxidation of methane at Gulf of Mexico cold seeps

The anaerobic oxidation of methane in aquatic environments is a globally significant sink for a potent greenhouse gas. Significant gaps remain in our understanding of the anaerobic oxidation of methane because data describing the distribution and abundance of putative anaerobic methanotrophs in relation to rates and patterns of anaerobic oxidation of methane activity are rare. An integrated biogeochemical, molecular ecological and organic geochemical approach was used to elucidate interactions between the anaerobic oxidation of methane, methanogenesis, and sulfate reduction in sediments from two cold seep habitats (one brine site, the other a gas hydrate site) along the continental slope in the Northern Gulf of Mexico. The results indicate decoupling of sulfate reduction from anaerobic oxidation of methane and the contemporaneous occurrence of methane production and consumption at both sites. Phylogenetic and organic geochemical evidence indicate that microbial groups previously suggested to be involved in anaerobic oxidation of methane coupled to sulfate reduction were present and active. The distribution and isotopic composition of lipid biomarkers correlated with microbial distributions, although concrete assignment of microbial function based on biomarker profiles was complicated given the observed overlap of competing microbial processes. Contemporaneous activity of anaerobic oxidation of methane and bicarbonate-based methanogenesis, the distribution of methane-oxidizing microorganisms, and lipid biomarker data suggest that the same microorganisms may be involved in both processes.     

Copper in surface waters of the Bering Sea

Copper concentrations have been measured in surface <75 m waters of the central Bering Sea. Concentrations of 2–4 nmole kg^?1 were measured in the Zhemchung Canyon region where water depths are greater than 1000 m. Concentrations are higher 2–25 nmole kg^?1 on the shallow <100 m continental shelf, inshore of a hydrographic front at the 100 m isobath. Copper-depth profiles on the continental shelf water mass are dominated by Cu concentrations increasing toward the sediments. These trends may be maintained by a flux of Cu from surficial sediments. A frontal system over the 100 m isobath acts to control the flux of Cu, a significant part of which apparently emanates from the sediments, between the continental shelf and the central Bering Sea basin. The benthic shelf Cu flux was constrained to be less than 3 nmole cm^?2 yr^?1.     

Diagnostic lipid biomarker and stable carbon isotope signatures of microbial communities mediating the anaerobic oxidation of methane with sulphate

The anaerobic oxidation of methane (AOM) with sulphate is the most important sink for methane in marine environments. This process is mediated by a consortium of methanotrophic archaea and sulphate reducing bacteria. So far, three groups of anaerobic methane oxidisers (ANME-1, -2 and -3) related to the methanogenic Methanosarcinales and Methanomicrobiales were discovered. The sulphate reducing partner of ANME-1 and -2 are two different eco-types of SRB related to the Desulfosarcina/Desulfococcus cluster (Seep-SRB1), whereas ANME-3 is associated with Desulfobulbus spp. (DBB). In this article, we reviewed literature data to assign statistically significant lipid biomarker signatures for a chemotaxonomic identification of the three known AOM communities. The lipid signatures of ANME-2/Seep-SRB1 and ANME-3/DBB are intriguingly similar, whereas ANME-1/Seep-SRB1 shows substantial differences to these AOM communities. ANME-1 can be distinguished from ANME-2 and -3 by a low ratio of the isoprenoidal dialkyl glycerol diethers sn2-hydroxyarchaeol and archaeol combined with a comparably low stable carbon isotope difference of archaeol relative to the source methane. Furthermore, only ANME-1 contains substantial amounts of isoprenoidal glycerol dialkyl glycerol tetraethers (GDGTs), however, with the probable exception of the ANME-2c sub-cluster. In contrast to the ANME-1 archaea, the tail to tail linked hydrocarbon tetramethylhexadecane (crocetane) is unique to ANME-2, whereas pentamethylicosenes (PMIs) with 4 and 5 double bonds without any higher saturated homologues were only found in ANME-3. The sulphate reducing partner of ANME-1 can be discerned from those of ANME-2 and -3 by a low ratio of the fatty acids (FAs) C_16:1ω5 relative to i-C_15:0 and, although to a lesser degree, by a high abundance of ai-C_15:0 relative to i-C_15:0. Furthermore, substantial amounts of ¹³C depleted non-isoprenoidal monoalkyl glycerol ethers (MAGEs) were only found in the sulphate reducing partners of ANME-2 and -3. A differentiation of these SRB is possible based on the characteristic presence of the FAs cy-C_17:0ω5,6 and C_17:1ω6, respectively. Generally, the data analysed here show overlaps between the different AOM communities, which highlights the need to use multiple lipid signatures for a robust identification of the dominating microbes involved.     

Carbonate formation by anaerobic oxidation of methane: Evidence from lipid biomarker and fossil 16S rDNA

Carbonate chimneys and other carbonate structures occur widespread in the Gulf of Cadiz and probably reflect the presence of cold seeps and associated release of methane in the geological past, possibly in the Early Pleistocene, but it is unclear under what conditions and by which processes these carbonates were formed. We studied a fossil methane-related carbonate crust collected from the Kidd mud volcano in the gulf. Concentrations of microbial lipids, their stable carbon isotope composition, sequences of fossil 16S rRNA genes of anaerobic methanotrophic archaea in combination with mineralogical and carbon and oxygen isotopic composition of carbonate were obtained for seven different horizons of the crust. This combination of organic and inorganic geochemical techniques with molecular ecological methods gave a consistent view on processes resulting in the formation of the crust and indicated that it took place in two phases and in a downward direction. Archaeal lipid biomarkers and fossil 16S rRNA gene sequence data revealed the dominance of archaeal ANME-2 group and elevated methane partial pressures during the formation of the top part of the crust. The lower part of the carbonate was likely formed in an environment with reduced methane fluxes as revealed by the dominance of fossil remains of ANME-1 archaea. The combination of these methods can be used as an effective tool to reconstruct in unprecedented detail the palaeo-biogeochemical processes resulting in the formation of carbonate fabrics. This interdisciplinary strategy may also be applied for other fossil methane-derived carbonates, generating new concepts and knowledge about past methane-related carbonate systems.     

Variscan orogeny in the Black Sea region

International Journal of Earth Sciences - Two Gondwana-derived Paleozoic belts rim the Archean/Paleoproterozoic nucleus of the East European Platform in the Black Sea region. In the north is a belt...