Description: There is growing concern about the transfer of methane originating from water bodies to the atmosphere. Methane from sediments can reach the atmosphere directly via bubbles or indirectly via vertical turbulent transport. This work quantifies methane gas bubble dissolution using a combination of bubble modeling and acoustic observations of rising bubbles to determine what fraction of the methane transported by bubbles will reach the atmosphere. The bubble model predicts the evolving bubble size, gas composition, and rise distance and is suitable for almost all aquatic environments. The model was validated using methane and argon bubble dissolution measurements obtained from the literature for deep, oxic, saline water with excellent results. Methane bubbles from within the hydrate stability zone (typically below 500 m water depth in the ocean) are believed to form an outer hydrate rim. To explain the subsequent slow dissolution, a model calibration was performed using bubble dissolution data from the literature measured within the hydrate stability zone. The calibrated model explains the impressively tall flares (〉1300 m) observed in the hydrate stability zone of the Black Sea. This study suggests that only a small amount of methane reaches the surface at active seep sites in the Black Sea, and this only from very shallow water areas (〈100 m). Clearly, the Black Sea and the ocean are rather effective barriers against the transfer of bubble methane to the atmosphere, although substantial amounts of methane may reach the surface in shallow lakes and reservoirs.

Description: High concentrations of free C32 bis-homohopanoic acids (up to 433 μg/g dry wt) occur in microbial mats at methane seeps in anoxic Black Sea waters. These compounds show a strong preference for the ‘geological’ 17α(H),21β(H)- over the ‘biological’ 17β(H),21β(H)-configuration (αβ/ββ ratios up to 30.7) and indicate the potential formation of αβ-hopanoids in modern environments. Strong 13C-depletions (δ13C as low as −78.4‰ PDB) indicate an in situ generation of these hopanoids by biota involved in the anaerobic cycling of methane carbon. The inferred presence of hopanoids indigenous to a permanently anoxic marine environment is significant because these lipids are not known to occur in strictly anaerobic bacteria.

Description: Carbonates recovered from anoxic waters between 235 and 1555 m depth in the northwestern Black Sea were analyzed for lipid biomarkers and stable carbon isotopic compositions. In addition, a methane-seep-related microbial mat and a sample of surface sediment recovered from a non-seep site were studied for comparison. High concentrations of strongly 13C-depleted lipids attributed to bacteria and archaea mediating the anaerobic oxidation of methane (AOM) were found in all samples except for the sediment. Differences of the dominant AOM-performing communities between the carbonates indicated by specific lipid patterns appear to be caused by the respective biogeochemical settings. High proportions of ANME-2 consortia are found at sites of assumingly high partial pressures of methane while ANME-1 associations dominate at locations of moderate methane supply. In the sedimentary concretion, a complex mixture of biomarkers for terrestrial and planktonic organisms was found. Different molecular structures along with strong variations in the stable carbon isotopic compositions (δ13C = − 20.2‰ to − 94.3‰) allow for an estimation of the proportions of tetraether-bound biphytanes derived from planktonic Crenarchaeota and methanotrophic Euryarchaeota. Our data imply that the shape of AOM-derived carbonate precipitates in Black Sea environments is crucially influenced by the respective methane supply. Active AOM-driven chimney-like bioherms, similar to those previously observed on the Ukrainian shelf, might also develop in the deep euxinic zone at 1555 m water depths.

Description: The abundance, activity, and temperature response of aerobic methane-oxidizing bacteria were studied in permafrost-affected tundra soils of northeast Siberia. The soils were characterized by both a high accumulation of organic matter at the surface and high methane concentrations in the water-saturated soils. The methane oxidation rates of up to 835 nmol CH4 h−1 g−1 in the surface soils were similar to the highest values reported so far for natural wetland soils worldwide. The temperature response of methane oxidation was measured during short incubations and revealed maximum rates between 22 °C and 28 °C. The active methanotrophic community was characterized by its phospholipid fatty acid (PLFA) concentrations and with stable isotope probing (SIP). Concentrations of 16:1ω8 and 18:1ω8 PLFAs, specific to methanotrophic bacteria, correlated significantly with the potential methane oxidation rates. In all soils, distinct 16:1 PLFAs were dominant, indicating a predominance of type I methanotrophs. However, long-term incubation of soil samples at 0 °C and 22 °C demonstrated a shift in the composition of the active community with rising temperatures. At 0 °C, only the concentrations of 16:1 PLFAs increased and those of 18:1 PLFAs decreased, whereas the opposite was true at 22 °C. Similarly, SIP with 13CH4 showed a temperature-dependent pattern. When the soils were incubated at 0 °C, most of the incorporated label (83%) was found in 16:1 PLFAs and only 2% in 18:1 PLFAs. In soils incubated at 22 °C, almost equal amounts of 13C label were incorporated into 16:1 PLFAs and 18:1 PLFAs (33% and 36%, respectively). We concluded that the highly active methane-oxidizing community in cold permafrost-affected soils was dominated by type I methanotrophs under in situ conditions. However, rising temperatures, as predicted for the future, seem to increase the importance of type II methanotrophs, which may affect methane cycling in northern wetlands.

Description: Highlights • Fatty acids preserved in an Oligocene whale bone were analysed. • The fatty acid content of the fossil was in the permil range vs. a recent whale vertebra. • Ca. 80% of the n-C16 and n-C18 alkyl moieties were extractable, ca. 20% being bound to kerogen. • Endogenous fatty acids were largely of microbial origin (sulfate reducers, actinobacteria). Abstract The taphonomic and diagenetic processes by which organic substances are preserved in animal remains are not completely known and the originality of putative metazoan biomolecules in fossil samples is a matter of scientific discussion. Here we report on biomarker information preserved in a fossil whale bone from an Oligocene phosphatic limestone (El Cien Fm., Mexico), with a focus on fatty acyl compounds. Extracts were quantitatively analysed using gas chromatography–mass spectrometry (GC–MS) and, to identify macromolecular-linked remains, demineralised extraction residues were subjected to catalytic hydropyrolysis (HyPy). To better recognise potential authentic (i.e. animal-derived) lipids, the data from the ancient bone were compared with those obtained from (i) the adjacent host sediment of the fossil and (ii) a recent whale (Phocoena phocoena) vertebra. In addition, the spatial distribution of organic and inorganic species was observed at the μm level by imaging MS (time-of-flight-secondary ion mass spectrometry, ToF-SIMS). Our results revealed a rather even distribution of hydrocarbon-, O- and N-containing ions in the trabecular network of the ancient bone. A different, more patchy arrangement of organic compounds was evident in the former marrow cavities that were partly cemented by clotted micrites of putative microbial origin. The concentration of fatty acids (FAs) in the ancient bone was in the permil range of the amount extracted from the recent whale vertebra. Endogenous compounds, including monoenoic n-C16 and n-C18 as well as branched FAs, were identified in the fossil bone by comparison with the host sediment. Ca. 80% of the prevalent n-C16 and n-C18 moieties in the ancient bone were extractable as FAs, whereas ca. 20% were covalently bound in the non-saponifiable kerogen fraction. Ample pyrite precipitates, distinctive 10-methyl branched FAs and microbial microborings (“tunneling”) indicate that sulfate reducers and collagen-degrading actinomycetes were central players in the microbial decomposition of the bone. Similarities with reported microbial FA patterns suggest that the FAs in the fossil bone were largely contributed by these microbial “last eaters”. The results highlight some of the degradation and preservation mechanisms during marine FA diagenesis in the “natural laboratory” of bones, and therefore the processes that lead to either degradation, preservation, or introduction of these widespread biomolecules in the fossils of ancient marine animals.

Description: High-resolution sedimentary records of major and minor elements (Al, Ba, Ca, Sr, Ti), total organic carbon (TOC), and profiles of pore water constituents (View the MathML sourceSO42-, CH4, Ca2+, Ba2+, Mg2+, alkalinity) were obtained for two gravity cores (core 755, 501 m water depth and core 214, 1686 m water depth) from the northwestern Black Sea. The records were examined in order to gain insight into the cycling of Ba in anoxic marine sediments characterized by a shallow sulfate–methane transition (SMT) as well as the applicability of barite as a primary productivity proxy in such a setting. The Ba records are strongly overprinted by diagenetic barite (BaSO4) precipitation and remobilization; authigenic Ba enrichments were found at both sites at and slightly above the current SMT. Transport reaction modeling was applied to simulate the migration of the SMT during the changing geochemical conditions after the Holocene seawater intrusion into the Black Sea. Based on this, sediment intervals affected by diagenetic Ba redistribution were identified. Results reveal that the intense overprint of Ba and Baxs (Ba excess above detrital average) strongly limits its correlation to primary productivity. These findings have implications for other modern and ancient anoxic basins, such as sections covering the Oceanic Anoxic Events which Ba is frequently used as a primary productivity indicator. Our study also demonstrates the limitations concerning the use of Baxs as a tracer for downward migrations of the SMT: due to high sedimentation rates at the investigated sites, diagenetic barite fronts are buried below the SMT within a relatively short period. Thus, ‘relict’ barite fronts would only be preserved for a few thousands of years, if at all.

Description: Carbonates are widespread at methane and petroleum seeps and are often precipitated as consequence of an alkalinity increase due to the anaerobic oxidation of methane (AOM) or, less often reported, of higher hydrocarbons. These carbonates are taphonomic windows into Earth's history, because they excellently protect the in situ formed microbial signatures (e.g. lipid biomarkers) from diagenetic destruction. A complication for paleoreconstructions, however, is that seep carbonates also encapsulate variable amounts of allochthonous organic matter, sometimes even completely obscuring authigenic microbial signatures. Seep carbonates from the Holocene Black Sea, the Pleistocene Enza River and the Pliocene San Lorenzo (both Northern Apennines, Italy) provide hints to better understand (i) the importance of processes other than AOM for the formation of seep carbonates and (ii) the controls of allochthonous and autochthonous contribution of biomarkers to organic matter in seep carbonates. Biomarker distributions in different parts of a Black Sea carbonate clearly demonstrate that high allochthonous organic matter is entrapped if AOM carbonates are formed intrasedimentary, particularly if methane supply is relatively low and external organic matter input high. High allochthonous contributions were also found in the biomarker inventory of ancient seep carbonates from the Italian Northern Apennines (Enza River and San Lorenzo) pointing at their precipitation within the sediment. Specific and complex conditions were indicated from our data for the Enza River location. Carbonate facies and particularly biomarker compositions, with abundant signatures of sulfate reducing bacteria, suggest that sulfate reduction using alkaline, and eventually sulfate- and higher hydrocarbon-enriched fluids triggered the growth of these seep carbonates. Our and other data suggest that this process has to be more considered if interpreting seep settings, particularly where microbial processes rely on rising fluids from deep petroleum reservoirs.

Description: Highlights • Four seafloor hydrocarbon emissions in the Eastern Black Sea were investigated • Eocene and/or Oligocene-Miocene Formations are most likely sources for oil and gas • Mixed secondary microbial and oil-associated thermogenic hydrocarbons at all sites • Site-specific light hydrocarbon compositions result from different mixing ratios Abstract 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 joint 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 to 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‰ 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 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.