Mineralogical and stable isotope analyses of carbonates from the eastern Black Sea

Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area ("Batumi seep area") located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups. X-ray diffractometry revealed the presence of two different authigenic carbonate phases, i.e. pure aragonitic rims associated with vital microbial mats and high-Mg calcite cementing the hemipelagic sediment. As indicated by the CT images, the initial sediment has been strongly deformed, first plastic then brittle, leading to brecciation of the progressively cemented sediment. The aragonitic rims on the other hand, represent a presumably recent carbonate growth phase since they cover the already deformed sediment. The stable oxygen isotope signature indicates that the high-Mg calcite cement incorporated pore water mixed with substantial hydrate water amounts. This points at a dominant role of high gas/fluid flux from decomposing gas hydrates leading to the deformation and cementation of the overlying sediment. In contrast, the aragonitic rims do not show an influence of 18O-enriched hydrate water. The differences in d18O between the presumably recent aragonite precipitates and the older high-Mg cements suggest that periods of hydrate dissociation and vigorous fluid discharge alternated with times of hydrate stability and moderate fluid flow. These results indicate that shallow-buried gas hydrates are prone to episodic decomposition with associated vigorous fluid flow. This might have a profound impact on the seafloor morphology resulting e.g. in the formation of carbonate pavements and pockmark-like structures but might also affect the local carbon cycle.

Active methane seepage in the Southern Ocean, off the sub-Antarctic island of South Georgia

An extensive submarine cold-seep area was discovered on the northern shelf of South Georgia during R/V Polarstern cruise ANT-XXIX/4 in spring 2013. Hydroacoustic surveys documented the presence of 133 gas bubble emissions, which were restricted to glacially-formed fjords and troughs. Video-based sea floor observations confirmed the sea floor origin of the gas emissions and spatially related microbial mats. Effective methane transport from these emissions into the hydrosphere was proven by relative enrichments of dissolved methane in near-bottom waters. Stable carbon isotopic signatures pointed to a predominant microbial methane formation, presumably based on high organic matter sedimentation in this region. Although known from many continental margins in the world's oceans, this is the first report of an active area of methane seepage in the Southern Ocean. Our finding of substantial methane emission related to a trough and fjord system, a topographical setting that exists commonly in glacially-affected areas, opens up the possibility that methane seepage is a more widespread phenomenon in polar and sub-polar regions than previously thought.

Mineralogical, geochemical, and lipid biomarker study of cabonate precipitates at station GeoB9908-1

Carbonate precipitates recovered from 2,000 m water depth at the Dolgovskoy Mound (Shatsky Ridge, north eastern Black Sea) were studied using mineralogical, geochemical and lipid biomarker analyses. The carbonates differ in shape from simple pavements to cavernous structures with thick microbial mats attached to their lower side and within cavities. Low d13C values measured on carbonates (-41 to -32 per mill V-PDB) and extracted lipid biomarkers indicate that anaerobic oxidation of methane (AOM) played a crucial role in precipitating these carbonates. The internal structure of the carbonates is dominated by finely laminated coccolith ooze and homogeneous clay layers, both cemented by micritic high-magnesium calcite (HMC), and pure, botryoidal, yellowish low-magnesium calcite (LMC) grown in direct contact to microbial mats. d18O measurements suggest that the authigenic HMC precipitated in equilibrium with the Black Sea bottom water while the yellowish LMC rims have been growing in slightly 18O-depleted interstitial water. Although precipitated under significantly different environmental conditions, especially with respect to methane availability, all analysed carbonate samples show lipid patterns that are typical for ANME-1 dominated AOM consortia, in the case of the HMC samples with significant contributions of allochthonous components of marine and terrestrial origin, reflecting the hemipelagic nature of the primary sediment.

Lucky Strike records of hydrothermal outflow temperatures

We deployed autonomous temperature sensors at black smoker chimneys, cracks, and diffuse flow areas at the Lucky Strike hydrothermal field (Mid-Atlantic Ridge, ~37°17'N) between summer 2009 and summer 2012 and contemporaneously measured tidal pressures and currents as part of the long-term MoMAR experiment to monitor hydrothermal activity. We classify the temperature data according to the hydrogeologic setting of the measurement sites: a high-temperature regime (>190°C) representing discharge of essentially unmixed, primary hydrothermal fluids through chimneys, an intermediate-temperature regime (10-100°C) associated with mixing of primary fluids with cold pore fluids discharging through cracks, and a low-temperature regime (<10°C) associated with a thermal boundary layer forming over bacterial mats associated with diffuse outflow of warm fluids. Temperature records from all the regimes exhibit variations at semi-diurnal tidal periods, and cross-spectral analyses reveal that high-temperature discharge correlates to tidal pressure while low-temperature discharge correlates to tidal currents. Intermediate-temperature discharge exhibits a transitional behavior correlating to both tidal pressure and currents. Episodic perturbations, with transient temperature drops of up to ~150°C, which occur in the high-temperature and intermediate-temperature records, are not observed on multiple probes (including nearby probes at the same site), and they are not correlated with microearthquake activity, indicating that the perturbation mechanism is highly localized at the measurement sites within the hydrothermal structures. The average temperature at a given site may increase or decrease at annual time scales, but the average temperature of the hydrothermal field, as a whole, appears to be stable over our 3 year observation period.