Batumi Seep Area Research Articles

Oil and gas seepage offshore Georgia (Black Sea) – Geochemical evidences for a paleogene-neogene hydrocarbon source rock

Numerous hydrocarbon seep sites at the continental shelf, slope, and in the deep water basin are known to feed the Black Sea water reservoir of dissolved methane. In this study, we identified the likely sources of gas and oil that are emitted at four sites located on the continental slope offshore Georgia in the Eastern Black Sea at 830 to 1,140 m water depth – an area with gas seepage only (Batumi seep area) and three areas of coupled gas and oil seepage (Iberia Mound, Colkheti Seep, and Pechori Mound). The geochemistry of bulk parameters, organic fractions and individual hydrocarbon biomarkers in near-surface sediments and of gas/oil expelled from the seafloor was analyzed and jointly interpreted to assign most likely hydrocarbon source rocks in the studied region. Presence of oleanane in shallow oil-impregnated sediments and oil slicks attests that the source rock at all sites is younger than Mid Cretaceous in age. We conclude that hydrocarbons ascending at all the four seepage areas originate from the Eocene Kuma Formation and/or the Oligocene–Lower Miocene Maikop Group, which are considered the principal hydrocarbon sources in the Eastern Black Sea region. Distributions of crude oil biomarkers in shallow sediments suggests moderate to heavy biodegradation. C1/C2+ ratios (10–4,163) along with stable C and H isotopic ratios (δ13C–CH4 ‒46.3 to −53.1.3‰ V-PDB; δ2H–CH4 ‒159 to −178‰ V-SMOW) indicate gas mixtures of oil-associated thermogenic and secondary microbial light hydrocarbons that are discharged from the four seep sites. Light hydrocarbons discharged at the Batumi Seep area are characterized by significant enrichments of methane, but have almost similar δ13C–CH4 values if compared to the other study sites. Such methane enrichments likely result from a comparably higher degree of petroleum degradation and associated formation of secondary microbial methane.

Can hydrocarbons entrapped in seep carbonates serve as gas geochemistry recorder?

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.

High-intensity gas seepage causes rafting of shallow gas hydrates in the southeastern Black Sea

Submarine gas hydrates are a major global reservoir of the potent greenhouse gas methane. Since current assessments of worldwide hydrate-bound carbon vary by one order of magnitude, new technical efforts are required for improved and accurate hydrate quantifications. Here we present hydrate abundances determined for surface sediments at the high-flux Batumi seep area in the southeastern Black Sea at 840 m water depth using state-of-the art autoclave technology. Pressure sediment cores of up to 2.65 m in length were recovered with an autoclave piston corer backed by conventional gravity cores. Quantitative core degassing yielded volumetric gas/bulk sediment ratios of up to 20.3 proving hydrate presence. The cores represented late glacial to Holocene hemipelagic sediments with the shallowest hydrates found at 90 cmbsf. Calculated methane concentrations in the different cores surpassed methane equilibrium concentrations in the two lowermost lithological Black Sea units sampled. The results indicated hydrate fractions of 5.2% of pore volume in the sapropelic Unit 2 and mean values of 21% pore volume in the lacustrine Unit 3. We calculate that the studied area of ~ 0.5 km 2 currently contains about 11.3 kt of methane bound in shallow hydrates. Episodic detachment and rafting of such hydrates is suggested by a rugged seafloor topography along with variable thicknesses in lithologies. We propose that sealing by hydrate precipitation in coarse-grained deposits and gas accumulation beneath induces detachment of hydrate/sediment chunks. Floating hydrates will rapidly transport methane into shallower waters and potentially to the sea–atmosphere boundary. In contrast, persistent in situ dissociation of shallow hydrates appears unlikely in the near future as deep water warming by about 1.6 °C and/or decrease in hydrostatic pressure corresponding to a sea level drop of about 130 m would be required. Because hydrate detachment should be primarily controlled by internal factors in this area and in similar hydrated settings, it serves as source of methane in shallow waters and the atmosphere which is mainly decoupled from external forcing.

Sources of fluids and gases expelled at cold seeps offshore Georgia, eastern Black Sea

Four seep sites located within an ∼20 km 2 area offshore Georgia (Batumi seep area, Pechori Mound, Iberia Mound, and Colkheti Seep) show characteristic differences with respect to element concentrations, and oxygen, hydrogen, strontium, and chlorine isotope signatures in pore waters, as well as impregnation of sediments with petroleum and hydrocarbon potential. All seep sites have active gas seepage, near surface authigenic carbonates and gas hydrates. Cokheti Seep, Iberia Mound, and Pechori Mound are characterized by oil-stained sediments and gas seepage decoupled from deep fluid advection and bottom water intrusion induced by gas bubble release. Pechori Mound is further characterized by deep fluid advection of lower salinity pore fluids. The Pechori Mound pore fluids are altered by mineral/water reactions at elevated temperatures (between 60 and 110 °C) indicated by heavier oxygen and lighter chlorine isotope values, distinct Li and B enrichment, and K depletion. Strontium isotope ratios indicate that fluids originate from late Oligocene strata. This finding is supported by the occurrence of hydrocarbon impregnations within the sediments. Furthermore, light hydrocarbons and high molecular weight impregnates indicate a predominant thermogenic origin for the gas and oil at Pechori Mound, Iberia Mound, and Colkheti Seep. C 15+ hydrocarbons at the oil seeps are allochtonous, whereas those at the Batumi seep area are autochthonous. The presence of oleanane, an angiosperm biomarker, suggests that the hydrocarbon source rocks belong to the Maikopian Formation. In summary, all investigated seep sites show a high hydrocarbon potential and hydrocarbons of Iberia Mound, Colkheti Seep, and Pechori Mound are predominantly of thermogenic origin. However, only at the latter seep site advection of deep pore fluids is indicated.

Authigenic carbonates from the eastern Black Sea as an archive for shallow gas hydrate dynamics – Results from the combination of CT imaging with mineralogical and stable isotope analyses

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 δ 18O 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.

Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone. Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C1–C4, CO2]). Molecular ratios of LMWHC (C1/[C2 + C3] > 1000) and stable isotopic compositions of methane (δ13C = − 53.5‰ V-PDB; D/H around − 175‰ SMOW) indicated predominant microbial methane formation. C1/C2+ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C1–C4, CO2]) relative to the other gas types and the virtual lack of 14C–CH4 indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely. As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C1–C4, CO2)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of 14C–CH4 (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.