Description: The geochemistry of seep gases is useful for an understanding of the local petroleum system. Here it was tested whether individual light hydrocarbons in seep gases are representatively entrapped in authigenic carbonates that formed near active seep sites. If applicable, it would be possible to extract geochemical information not only on the origin but also on the thermal maturity of the hydrocarbon source rocks from the gases entrapped in carbonates in the past. Respective data could be used for a better understanding of paleoenvironments and might directly serve as calibration point for, amongst others, petroleum system modeling. For this approach, (sub)-recent seep carbonates from the Black Sea (Paleodnjepr region and Batumi seep area), two sites of the Campeche Knoll region in the Gulf of Mexico, and the Venere mud volcano (Mediterranean Sea) were selected. These seep carbonates derive from sites for which geochemical data on the currently seeping gases exist. During treatment with phosphoric acid, methane and higher hydrocarbons were released from all carbonates, but in low concentrations. Compositional studies demonstrate that the ratio of methane to the sum of higher hydrocarbons (C1/(C2+C3)) is (partly strongly) positively biased in the entrapped gas fraction. δ13C values of C1 were determined for all samples and, for the samples from the Gulf of Mexico and the Mediterranean Sea, also of C2 and C3. The present dataset from six seep sites indicates that information on the seeped methane can be—although with a scatter of several permil—recorded in seep carbonate matrices, but other valuable information like the composition and δ13C of ethane and propane appears to be modified or lost during, for example, enclosure or at an early stage of diagenesis.

Description: The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.

Description: Delineation of stratigraphic sequences and their component systems tracts in mudstone-dominated successions is challenging due to the relatively homogenous, fine-grained nature of the strata. High-resolution elemental intensity data from X-ray fluorescence core scanning is used in order to develop a sequence stratigraphic framework for the Lower Cretaceous monotonous mudstone succession in the eastern Lower Saxony Basin. The study is based on four drill cores covering the Berriasian to Aptian interval. In addition, carbon isotope (δ13Corg), grain size and CaCO3 analyses were carried out on discrete samples. The studied cores represent both proximal and distal basinal environments of the eastern Lower Saxony Basin and can be reliably correlated by utilizing variations in selected X-ray fluorescence elemental ratios, K/Ti data have proven to be particularly suitable in this regard. The core correlation shows that chemostratigraphic variability within the studied succession is laterally reproducible in the eastern Lower Saxony Basin, and can be used to establish a sequence stratigraphic framework. Further, Si/Al and Ca/Ti ratios have been applied to characterize the cores in terms of variation in grain size and CaCO3 content, respectively. Vertical grading trends inferred from Si/Al changes were used to identify transgressive and regressive systems tracts within the studied succession. An important regression in the uppermost lower Valanginian coincides with the onset of the Valanginian Weissert Event, as indicated by the well-known positive δ13C shift, and, thus, supports the idea that the initial interval of this event corresponds to enhanced supply of terrigenous material. The results of this study are also in agreement with previously recognized transgressive-regressive trends in the Lower Saxony Basin and adjacent areas. This clearly shows that systematic geochemical variations recorded in mudstone-dominated basinal settings are suitable to establish sequence stratigraphic frameworks.