Rare earth elements of modern seeps from the Gulf of Mexico, the Black Sea, and the Congo Fan

At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (SumREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the SumREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that SumREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.

Gas emissions and ROV survey tracks of the Regab pockmark (Northern Congo Fan)

Pockmarks are seafloor depressions commonly associated with fluid escape from the seabed and are believed to contribute noticeably to the transfer of methane into the ocean and ultimately into the atmosphere. They occur in many different areas and geological contexts, and vary greatly in size and shape. Nevertheless, the mechanisms of pockmark growth are still largely unclear. Still, seabed methane emissions contribute to the global carbon budget, and understanding such processes is critical to constrain future quantifications of seabed methane release at local and global scales. The giant Regab pockmark (9°42.6' E, 5°47.8' S), located at 3160 m water depth near the Congo deep-sea channel (offshore southwestern Africa), was investigated with state-of-the-art mapping devices mounted on IFREMER's (French Research Institute for Exploitation of the Sea) remotely operated vehicle (ROV) Victor 6000. ROV-borne micro-bathymetry and backscatter data of the entire structure, a high-resolution photo-mosaic covering 105,000 m2 of the most active area, sidescan mapping of gas emissions, and maps of faunal distribution as well as of carbonate crust occurrence are combined to provide an unprecedented detailed view of a giant pockmark. All data sets suggest that the pockmark is composed of two very distinctive zones in terms of seepage intensity. We postulate that these zones are the surface expression of two fluid flow regimes in the subsurface: focused flow through a fractured medium and diffuse flow through a porous medium. We conclude that the growth of giant pockmarks is controlled by self-sealing processes and lateral spreading of rising fluids. In particular, partial redirection of fluids through fractures in the sediments can drive the pockmark growth in preferential directions.

Specific microbial biomarker signatures from Congo fan sediments of ODP site 175-1075, Congo soils, wetland and estuary sediments

Methane (CH4) is a strong greenhouse gas known to have perturbed global climate in the past, especially when released in large quantities over short time periods from continental or marine sources. It is therefore crucial to understand and, if possible, quantify the individual and combined response of these variable methane sources to natural climate variability. However, past changes in the stability of greenhouse gas reservoirs remain uncertain and poorly constrained by geological evidence. Here, we present a record from the Congo fan of a highly specific bacteriohopanepolyol (BHP) biomarker for aerobic methane oxidation (AMO), 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), that identifies discrete periods of increased AMO as far back as 1.2 Ma. Fluctuations in the concentration of aminopentol, and other 35-aminoBHPs, follow a pattern that correlates with late Quaternary glacial-interglacial climate cycles, with highest concentrations during warm periods. We discuss possible sources of aminopentol, and the methane consumed by the precursor methanotrophs, within the context of the Congo River setting, including supply of methane oxidation markers from terrestrial watersheds and/or marine sources (gas hydrate and/or deep subsurface gas reservoir). Compound-specific carbon isotope values of -30 per mil to -40 per mil for BHPs in ODP 1075 and strong similarities between the BHP signature of the core and surface sediments from the Congo estuary and floodplain wetlands from the interior of the Congo River Basin, support a methanotrophic and likely terrigenous origin of the 35-aminoBHPs found in the fan sediments. This new evidence supports a causal connection between marine sediment BHP records of tropical deep sea fans and wetland settings in the feeding river catchments, and thus tropical continental hydrology. Further research is needed to better constrain the different sources and pathways of methane emission. However, this study identifies the large potential of aminoBHPs, in particular aminopentol, to trace and, once better calibrated and understood, quantify past methane sources and fluxes from terrestrial and potentially also marine sources.

Pore water (SO4, CH4, alkalinity, HS-, Ca, Sr, Mg, Ba) and solid phase (Ca, Sr, Mg, Ba) data measured in pockmark sediments of the Northern Congo Fan

This study focuses on the vertical distribution of authigenic carbonates (aragonite and high Mg-calcite) in the form of finely disseminated precipitates as well as massive carbonate concretions present in and above gas hydrate bearing sediments of the Northern Congo Fan. Analyses of Ca, Mg, Sr and Ba in pore water, bulk sediments and authigenic carbonates were carried out on gravity cores taken from three pockmark structures (Hydrate Hole, Black Hole and Worm Hole). In addition, a background core was retrieved from an area not influenced by fluid seepage. Pore water Sr/Ca and Mg/Ca ratios are used to reveal the current depths of carbonate formation as well as the mineralogy of the authigenic precipitates. The Sr/Ca and Mg/Ca ratios of bulk sediments and massive carbonate concretions were applied to infer the presence and depth distribution of authigenic aragonite and high Mg-calcite, based on the approach presented by Bayon et al. [Bayon et al. (2007). Sr/Ca and Mg/Ca ratios in Niger Delta sediments: Implications for authigenic carbonate genesis in cold seep environments. Marine Geology 241(1-4), 93-109, doi:10.1016/j.margeo.2007.03.007]. We show that the approach developed by Bayon et al. (2007) for sediments of cold seeps of the Niger Delta is also suitable to identify the mineralogy of authigenic carbonates in pockmark sediments of the Congo Deep-Sea Fan. We expand this approach by combining interstitial with solid phase Sr/Ca and Mg/Ca ratios, which demonstrate that high Mg-calcite is the predominant authigenic carbonate that currently forms at the sulfate/methane reaction zone (SMRZ). This is the first study which investigates both solid phase and pore water signatures typical for either aragonite or high Mg-calcite precipitation for the same sediment cores and thus is able to identify active and fossil carbonate precipitation events. At all investigated pockmark sites fossil horizons of the SMRZ were deduced from high Mg-calcite located above and below the current depths of the SMRZ. Additionally, aragonite enrichments typical for high seepage rates were detected close to the sediment surface at these sites. However, active precipitation of aragonite as indicated by pore water characteristics only occurs at the Black Hole site. Dissolved and solid phase Ba concentrations were used to estimate the time the SMRZ was fixed at the current depths of the diagenetic barite fronts. The combined pore water and solid phase elemental ratios (Mg/Ca, Sr/Ca) and Ba concentrations allow the reconstruction of past changes in methane seepage at the investigated pockmark sites. At the Hydrate Hole and Worm Hole sites the time of high methane seepage was estimated to have ceased at least 600 yr BP. In contrast, a more recent change from a high flux to a more dormant stage must have occurred at the Black Hole site as evidenced by active aragonite precipitation at the sediment surface and a lack of diagenetic Ba enrichments.

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.