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.

Biogeochemical measurements associated to deep-sea wood falls

Large organic food falls to the deep sea - such as whale carcasses and wood logs - support the development of reduced, sulfidic niches in an otherwise oxygenated, oligotrophic deep-sea environment. These transient hot spot ecosystems may serve the dispersal of highly adapted chemosynthetic organisms such as thiotrophic bivalves and siboglinid worms. Here we investigated the biogeochemical and microbiological processes leading to the development of sulfidic niches. Wood colonization experiments were carried out for the duration of one year in the vicinity of a cold seep area in the Nile deep-sea fan (Eastern Mediterranean) at depths of 1690 m. Wood logs were deployed in 2006 during the BIONIL cruise (RV Meteor M70/2 with ROV Quest, Marum, Germany) and sampled in 2007 during the Medeco-2 cruise (RV Pourquoi Pas? with ROV Victor 6000, Ifremer, France). Wood-boring bivalves played a key role in the initial degradation of the wood, the dispersal of wood chips and fecal matter around the wood log, and the provision of colonization surfaces to other organisms. Total oxygen uptake measured with a ROV-operated benthic chamber module was higher at the wood (0.5 m away) in contrast to 10 m away at a reference site (25 mmol m-2 d-1 and 1 mmol m-2 d-1, respectively), indicating an increased activity of sedimentary communities around the wood falls. Bacterial cell numbers associated with wood increased substantially from freshly submerged wood to the wood chip/fecal matter layer next to the wood experiments, as determined with Acridine Orange Direct Counts (AODC) and DAPI-stained counts. Microsensor measurements of sulfide, oxygen and pH were conducted ex situ. Sulfide fluxes were higher at the wood experiments when compared to reference measurements (19 and 32 mmol m-2 d-1 vs. 0 and 16 mmol -2 d-1, respectively). Sulfate reduction (SR) rates at the wood experiments were determined in ex situ incubations (1.3 and 2.0 mmol m-2 d-1) and fell into the lower range of SR rates previously observed from other chemosynthetic habitats at cold seeps. There was no influence of wood deposition on phosphate, silicate and nitrate concentrations, but ammonium concentrations were elevated at the wood chip-sediment boundary layer. Concentrations of dissolved organic carbon were much higher at the wood experiments (wood chip-sediment boundary layer) in comparison to measurements at the reference sites, which may indicate that cellulose degradation was highest under anoxic conditions and hence enabled by anaerobic benthic bacteria, e.g. fermenters and sulfate reducers. Our observations demonstrate that, after one year, the presence of wood at the seafloor had led to the creation of sulfidic niches, comparable to what has been observed at whale falls, albeit at lower rates.

Shapefile of the survey tracks of 'Mosaic 02' at the Regab pockmark (Northern Congo Fan)

The Regab pockmark is a large cold seep area located 10 km north of the Congo deep sea channel at about 3160 m water depth. The associated ecosystem hosts abundant fauna, dominated by chemosynthetic species such as the mussel Bathymodiolus aff. boomerang, vestimentiferan tubeworm Escarpia southwardae, and vesicomyid clams Laubiericoncha chuni and Christineconcha regab. The pockmark was visited during the West African Cold Seeps (WACS) cruise with RV Pourquoi Pas? in February 2011, and a 14,000-m**2 high-resolution videomosaic was constructed to map the most populated area and to describe the distribution of the dominant megafauna (mussels, tubeworms and clams). The results are compared with previous published works, which also included a videomosaic in the same area of the pockmark, based on images of the BIOZAIRE cruise in 2001. The 10-year variation of the faunal distribution is described and reveals that the visible abundance and distribution of the dominant megafaunal populations at Regab have not changed significantly, suggesting that the overall methane and sulfide fluxes that reach the faunal communities have been stable. Nevertheless, small and localized distribution changes in the clam community indicate that it is exposed to more transient fluxes than the other communities. Observations suggest that the main megafaunal aggregations at Regab are distributed around focused zones of high flux of methane-enriched fluids likely related to distinct smaller pockmark structures that compose the larger Regab pockmark. Although most results are consistent with the existing successional models for seep communities, some observations in the distribution of the Regab mussel population do not entirely fit into these models. This is likely due to the high heterogeneity of this site formed by the coalescence of several pockmarks. We hypothesize that the mussel distribution at Regab could also be controlled by the occurrence of zones of both intense methane fluxes and reduced efficiency of the anaerobic oxidation of methane possibly limiting tubeworm colonization.

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.