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  • 1
    Publication Date: 2017-06-27
    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.
    Type: Article , PeerReviewed
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  • 2
    Publication Date: 2017-06-28
    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.
    Type: Article , PeerReviewed
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  • 3
    Publication Date: 2018-07-18
    Description: Mixing processes of reduced hydrothermal fluids with oxygenated seawater and fluid-rock reactions contribute to the chemical signatures of diffuse venting and likely determine the geochemical constraints on microbial life. We examined the influence of fluid chemistry on microbial diversity and activity by sampling diffuse fluids emanating through mussel beds at two contrasting hydrothermal vents. The H(2) concentration was very low at the basalt-hosted Clueless site, and mixing models suggest O(2) availability throughout much of the habitat. In contrast, effluents from the ultramafic-hosted Quest site were considerably enriched in H(2) , while O(2) is likely limited to the mussel layer. Only two different hydrogenase genes were identified in clone libraries from the H(2) -poor Clueless fluids, but these fluids exhibited the highest H(2) uptake rates in H(2) -spiked incubations (oxic conditions, at 18 °C). In contrast, a phylogenetically diverse H(2) -oxidizing potential was associated with distinct thermal conditions in the H(2) -rich Quest fluids, but under oxic conditions, H(2) uptake rates were extremely low. Significant stimulation of CO(2) fixation rates by H(2) addition was solely illustrated in Quest incubations (P-value 〈0.02), but only in conjunction with anoxic conditions (at 18 °C). We conclude that the factors contributing toward differences in the diversity and activity of H(2) oxidizers at these sites include H(2) and O(2) availability.
    Type: Article , PeerReviewed
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  • 4
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    Elsevier
    In:  Palaeogeography Palaeoclimatology Palaeoecology, 227 (1-3). pp. 31-47.
    Publication Date: 2017-06-30
    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.
    Type: Article , PeerReviewed
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  • 5
    Publication Date: 2020-06-12
    Description: Halocarbons are important vectors of reactive halogens to the atmosphere, where the latter participate in several chemical key processes. Many efforts have been made to quantify their sources and sinks. However, those are still designated to large uncertainties. In contrast to other coastal habitats such as salt marshes and kelp communities, seagrass meadows have so far not been investigated with regard to trace gases. In order to study seagrass meadows as a potential source for halocarbons to the atmosphere, we conducted dynamic flux chamber measurements at a coastal site in List/Sylt, Northern Germany. Emissions of halocarbons from seagrass meadows into the atmosphere were found for chloromethane (CH3Cl), bromomethane (CH3Br), iodomethane (CH3I), and bromoform (CHBr3) being the main compounds, while the sediment seems to be a net sink for CH3Cl and CH3Br. Stable carbon isotopes of halocarbons were determined using a newly developed comprehensive coupled isotope and mass balance for dynamic flux chambers. Mean stable carbon isotope compositions of the emitted halocarbons were -50‰ (CH3Cl), -52‰ (CH3Br), -63‰ (CH3I) and -14‰ (CHBr3).
    Type: Article , PeerReviewed
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  • 6
    Publication Date: 2017-02-09
    Description: Hydrothermal emission of mantle helium appears to be directly related to magma production rate, but other processes can generate methane and hydrogen on mid-ocean ridges. In an on-going effort to characterize these processes in the South Atlantic, the flux and distribution of these gases were investigated in the vicinity of a powerful black smoker recently discovered at 8°17.9' S, 13°30.4' W. The vent lies on the shoulder of an oblique offset in the Mid-Atlantic Ridge and discharges high concentrations of methane and hydrogen. Measurements during expeditions in 2004 and 2006 show that the ratio of CH4 to 3He in the neutrally buoyant plume is quite high, 4 × 108. The CTD stations were accompanied by velocity measurements with lowered acoustic Doppler current profilers (LADCP), and from these data we estimate the methane transport to have been 0.5 mol s− 1 in a WSW-trending plume that seems to develop during the ebb tidal phase. This transport is an order of magnitude greater than the source of CH4 calculated from its concentration in the vent fluid and the rise height of the plume. From this range of methane fluxes, the source of 3He is estimated to be between 0.14 and 1.2 nmol s− 1. In either case, the 3He source is significantly lower than expected from the spreading rate of the Mid-Atlantic Ridge. From the inventory of methane in the rift valley adjacent to the vent, it appears that the average specific rate of oxidation is 2.6 to 23 yr− 1, corresponding to a turnover time between 140 and 16 days. Vertical profiles of methane in the surrounding region often exhibited Gaussian-like distributions, and the variances appear to increase with distance from the vent. Using a Gaussian plume model, we obtained a range of vertical eddy diffusivities between 0.009 and 0.08 m2m2 s− 1. These high values may be due to tidally driven internal waves across the promontory on which the vent is located.
    Type: Article , PeerReviewed
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  • 7
    Publication Date: 2015-11-24
    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.
    Type: Article , PeerReviewed
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  • 8
    Publication Date: 2017-05-09
    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.
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