Description: Hydrocarbon seeps are ubiquitous at gas-prone Cenozoic deltas such as the Nile Deep Sea Fan (NDSF2) where seepage into the bottom water has been observed at several mud volcanoes (MVs3) including North Alex MV (NAMV4). Here we investigated the sources of hydrocarbon gases and sedimentary organic matter together with biomarkers of microbial activity at four locations of NAMV to constrain how venting at the seafloor relates to the generation of hydrocarbon gases in deeper sediments. At the centre, high upward flux of hot (70 °C) hydrocarbon-rich fluids is indicated by an absence of biomarkers of Anaerobic Oxidation of Methane (AOM) and nearly constant methane (CH4) concentration depth-profile. The presence of lipids of incompatible thermal maturities points to mixing between early-mature petroleum and immature organic matter, indicating that shallow mud has been mobilized by the influx of deep-sourced hydrocarbon-rich fluids. Methane is enriched in the heavier isotopes, with values of δ13C∼−46.6‰VPDB and δD ∼−228‰VSMOW, and is associated with high amounts of heavier homologues (C2+) suggesting a co-genetic origin with the petroleum. On the contrary at the periphery, a lower but sustained CH4 flux is indicated by deeper sulphate–methane transition zones and the presence of 13C-depleted biomarkers of AOM, consistent with predominantly immature organic matter. Values of δ13C-CH4∼−60‰VPDB and decreased concentrations of 13C-enriched C2+ are typical of mixed microbial CH4 and biodegraded thermogenic gas from Plio-Pleistocene reservoirs of the region. The maturity of gas condensate migrated from pre-Miocene sources into Miocene reservoirs of the Western NDSF is higher than that of the gas vented at the centre of NAMV, supporting the hypothesis that it is rather released from the degradation of oil in Neogene reservoirs. Combined with the finding of hot pore water and petroleum at the centre, our results suggest that clay mineral dehydration of Neogene sediments, which takes place posterior to reservoir filling, may contribute to intense gas generation at high sedimentation rate deltas.

Description: Hydrocarbon seeps are ubiquitous at gas-prone Cenozoic deltas such as the Nile Deep Sea Fan (NDSF2) where seepage into the bottom water has been observed at several mud volcanoes (MVs3) including North Alex MV (NAMV4). Here we investigated the sources of hydrocarbon gases and sedimentary organic matter together with biomarkers of microbial activity at four locations of NAMV to constrain how venting at the seafloor relates to the generation of hydrocarbon gases in deeper sediments. At the centre, high upward flux of hot (70 °C) hydrocarbon-rich fluids is indicated by an absence of biomarkers of Anaerobic Oxidation of Methane (AOM) and nearly constant methane (CH4) concentration depth-profile. The presence of lipids of incompatible thermal maturities points to mixing between early-mature petroleum and immature organic matter, indicating that shallow mud has been mobilized by the influx of deep-sourced hydrocarbon-rich fluids. Methane is enriched in the heavier isotopes, with values of δ13C∼−46.6‰VPDB and δD ∼−228‰VSMOW, and is associated with high amounts of heavier homologues (C2+) suggesting a co-genetic origin with the petroleum. On the contrary at the periphery, a lower but sustained CH4 flux is indicated by deeper sulphate–methane transition zones and the presence of 13C-depleted biomarkers of AOM, consistent with predominantly immature organic matter. Values of δ13C-CH4∼−60‰VPDB and decreased concentrations of 13C-enriched C2+ are typical of mixed microbial CH4 and biodegraded thermogenic gas from Plio-Pleistocene reservoirs of the region. The maturity of gas condensate migrated from pre-Miocene sources into Miocene reservoirs of the Western NDSF is higher than that of the gas vented at the centre of NAMV, supporting the hypothesis that it is rather released from the degradation of oil in Neogene reservoirs. Combined with the finding of hot pore water and petroleum at the centre, our results suggest that clay mineral dehydration of Neogene sediments, which takes place posterior to reservoir filling, may contribute to intense gas generation at high sedimentation rate deltas. Highlights ► Extensive seepage of biodegraded gas at the periphery of North Alex mud volcano. ► At the centre seepage of deeper-sourced hot water, oil and thermogenic gas. ► At the centre, degradation of reservoired-oil to gas is most likely. ► Multivariate statistics on biomarkers show oil degradation at the centre and AOM at the periphery. ► Shallow gas production is enhanced by hot water influx from actively dewatering clays.

Description: Cold seeps in the Aleutian deep-sea trench support prolific benthic communities and generate carbonate precipitates which are dependent on carbon dioxide delivered from anaerobic methane oxidation. This process is active in the anaerobic sediments at the sulfate reduction-methane production boundary and is probably performed by archaea working in syntrophic co-operation with sulfate-reducing bacteria. Diagnostic lipid biomarkers of archaeal origin include irregular isoprenoids such as 2,6,11,15-tetramethylhexadecane (crocetane) and 2,6,10,15,19-pentamethylicosane (PMI) as well as the glycerol ether lipid archaeol (2,3-di-O-phytanyl-sn-glycerol). These biomarkers are prominent lipid constituents in the anaerobic sediments as well as in the carbonate precipitates. Carbon isotopic compositions of the biomarkers are strongly depleted in 13C with values of δ13C as low as −130.3‰ PDB. The process of anaerobic methane oxidation is also reflected in the carbon isotope composition of organic matter with δ13C-values of −39.2 and −41.8‰ and of the carbonate precipitates with values of −45.4 and −48.7‰. This suggests that methane-oxidizing archaea have accumulated within the microbial community, which is active at the cold seep sites. The dominance of crocetane in sediments at one station indicates that, probably due to decreased methane venting, archaea might no longer be growing, whereas high amounts of crocetenes found at other more active stations may indicate recent fluid venting and active archaea. Comparison with other biomarker studies suggests that various archaeal assemblages might be involved in the anaerobic consumption of methane. The assemblages are apparently dependent on specific conditions found at each cold seep environment. Selective conditions probably include water depth, temperature, degree of anoxia, and supply of free methane.

Description: Saanich Inlet has been a highly productive fjord since the last glaciation. During ODP Leg 169S, nearly 70 m of Holocene sediments were recovered from Hole 1034 at the center of the inlet. The younger sediments are laminated, anaerobic, and rich in organic material (1–2.5 wt.% Corg), whereas the older sediments below 70 mbsf are non-laminated, aerobic, with glacio-marine characteristics and have a significantly lower organic matter content. This difference is also reflected in the changes of interstitial fluids, and in biomarker compositions and their carbon isotope signals. The bacterially-derived hopanoid 17α(H),21β(H)-hop-22(29)-ene (diploptene) occurs in Saanich Inlet sediments throughout the Holocene but is not present in Pleistocene glacio-marine sediments. Its concentration increases after ∼6000 years BP up to present time to about 70 μg/g Corg, whereas terrigenous biomarkers such as the n-alkane C31 are low throughout the Holocene (〈51 μg/g Corg) and even slightly decrease to 36 μg/g Corg at the most recent time. The increasing concentrations of diploptene in sediments younger than ∼6000 years BP separate a recent period of higher primary productivity, stronger anoxic bottom waters, and higher bacterial activity from an older period with lesser activity, heretofore undifferentiated. Carbon isotopic compositions of diploptene in the Holocene are between −31.5 and −39.6‰ PDB after ∼6000 years BP. These differences in the carbon isotopic record of diploptene probably reflect changes in microbial community structure of bacteria living at the oxic–anoxic interface of the overlying water column. The heavier isotope values are consistent with the activity of nitrifying bacteria and the lighter isotope values with that of aerobic methanotrophic bacteria. Therefore, intermediate δ13C values probably represent mixtures between the populations. In contrast, carbon isotopic compositions of n-C31 are roughly constant at −31.4±1.1‰ PDB throughout the Holocene, indicating a uniform input from cuticular waxes of higher plants. Prior to ∼6000 years BP, diploptene enriched in 13C of up to −26.3‰ PDB is indicative of cyanobacteria living in the photic zone and suggests a period of lower primary productivity, more oxygenated bottom waters, and hence lower bacterial activity during the earliest Holocene.

Description: Highlights: • Constraining sources of core and intact archaeal lipids with stable C isotopic ratios. • No evidence for sedimentary sources of IPL crenarchaeol. • Evidence of sedimentary production of IPL caldarchaeol and BDGT-0. • Higher organic matter content promotes higher activity of sedimentary archaea. • Archaeol is a sensitive indicator of sedimentary archaea. Archaea occupy an important niche in the global carbon cycle and their lipids are widely used as indicators of environmental conditions in both paleoenvironmental and modern biogeochemical studies. The principal sources of archaeal lipids in marine sediments are benthic archaea, fossil remnants of planktonic archaea, and allochthonous sources such as soils. However, the relative contributions of these sources to the sedimentary lipid pool have not been comprehensively constrained, complicating a mechanistic understanding of archaeal lipid proxies. In order to provide insights into the relative contributions of these sources and identify signals derived from sedimentary activity, we performed a systematic survey of stable carbon isotopic compositions (delta C-13) of both core and intact archaeal lipids via analyses of their phytanyl (Phy) and biphytanyl (BP) moieties in diverse marine sediments. The sample set consisted of 44 sediment horizons from the Mediterranean and adjacent basins and represented diverse sources of organic matter and depositional conditions. Complementary geochemical data enabled the comparison of lipid distributions and carbon isotopic signatures with prevailing redox conditions. The delta C-13 of tricyclic BP (BPcren) from the core and intact forms of crenarchaeol ranged from -19.1 to -28.6% and -18.1 to -27.4%, respectively. delta C-13 values of core and intact BPcren did not differ, suggesting that intact crenarchaeol is either a fossil relic from planktonic archaea or a product of lipid recycling by benthic archaea, as opposed to being synthesized de novo by sedimentary archaea. delta C-13 values of BP0 derived from core and intact forms of glycerol and butanetriol dibiphytanyl glycerol tetraethers (GDGTs and BGDTs, respectively), but predominantly from caldarchaeol (GDGT-0), ranged from -19.4 to -32.0% and -20.9 to -37.0%, respectively. In contrast to BPcren, intact-lipid derived BP0 was often C-13-depleted relative to its core counterpart, consistent with in situ production by sedimentary archaea. This relative depletion was most pronounced in sulfate reduction zones, likely due to heterotrophic activity. Core and intact archaeol exhibited the largest ranges in delta C-13 values, from -21.6 to -42.1% and -22.7 to -58.9%, respectively. This strong C-13-depletion relative to both total organic carbon and dissolved inorganic carbon is consistent with mixtures of functional sources of sedimentary chemolithoautotrophic, methanotrophic, methanogenic and heterotrophic archaea. Based on the substantial C-13-depletion of BPcren and BP0 in samples in the vicinity of the Rhone River delta relative to a distal marine reference site, we infer that the terrestrial soil contribution of archaeal lipids to these sediments is as high as 43%. Hence, terrestrial input of archaeal lipids, including their intact forms, can be substantial and suggests caution when using existing molecular proxies aimed at constraining riverine input. In summary, our comparative isotopic analysis of sedimentary core versus intact archaeal lipids improves the apportionment of their diverse sources and confidence in distinguishing in situ lipid production by sedimentary archaea.

Description: © The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Frontiers in Microbiology 8 (2017): 702, doi:10.3389/fmicb.2017.00702.

Description: The unique geochemistry of marine shallow-water hydrothermal systems promotes the establishment of diverse microbial communities with a range of metabolic pathways. In contrast to deep-sea vents, shallow-water vents not only support chemosynthesis, but also phototrophic primary production due to the availability of light. However, comprehensive studies targeting the predominant biogeochemical processes are rare, and consequently a holistic understanding of the functioning of these ecosystems is currently lacking. To this end, we combined stable isotope probing of lipid biomarkers with an analysis of the bacterial communities to investigate if chemoautotrophy, in parallel to photoautotrophy, plays an important role in autotrophic carbon fixation and to identify the key players. The study was carried out at a marine shallow-water hydrothermal system located at 5 m water depth off Dominica Island (Lesser Antilles), characterized by up to 55°C warm hydrothermal fluids that contain high amounts of dissolved Fe2+. Analysis of the bacterial diversity revealed Anaerolineae of the Chloroflexi as the most abundant bacterial class. Furthermore, the presence of key players involved in iron cycling generally known from deep-sea hydrothermal vents (e.g., Zetaproteobacteria and Geothermobacter), supported the importance of iron-driven redox processes in this hydrothermal system. Uptake of 13C-bicarbonate into bacterial fatty acids under light and dark conditions revealed active photo- and chemoautotrophic communities, with chemoautotrophy accounting for up to 65% of the observed autotrophic carbon fixation. Relatively increased 13C-incorporation in the dark allowed the classification of aiC15:0, C15:0, and iC16:0 as potential lipid biomarkers for bacterial chemoautotrophy in this ecosystem. Highest total 13C-incorporation into fatty acids took place at the sediment surface, but chemosynthesis was found to be active down to 8 cm sediment depth. In conclusion, this study highlights the relative importance of chemoautotrophy compared to photoautotrophy in a shallow-water hydrothermal system, emphasizing chemosynthesis as a prominent process for biomass production in marine coastal environments influenced by hydrothermalism.

Description: SS was supported by NSF grant OCE-1124272. This work was financed through the DFG Emmy Noether Grant BU 2606/1-1 to SB.

Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Wagner, S., Schubotz, F., Kaiser, K., Hallmann, C., Waska, H., Rossel, P. E., Hansmann, R., Elvert, M., Middelburg, J. J., Engel, A., Blattmann, T. M., Catala, T. S., Lennartz, S. T., Gomez-Saez, G., V., Pantoja-Gutierrez, S., Bao, R., & Galy, V. Soothsaying DOM: A current perspective on the future of oceanic dissolved organic carbon. Frontiers in Marine Science, 7, (2020): 341, doi:10.3389/fmars.2020.00341.

Description: The vast majority of freshly produced oceanic dissolved organic carbon (DOC) is derived from marine phytoplankton, then rapidly recycled by heterotrophic microbes. A small fraction of this DOC survives long enough to be routed to the interior ocean, which houses the largest and oldest DOC reservoir. DOC reactivity depends upon its intrinsic chemical composition and extrinsic environmental conditions. Therefore, recalcitrance is an emergent property of DOC that is analytically difficult to constrain. New isotopic techniques that track the flow of carbon through individual organic molecules show promise in unveiling specific biosynthetic or degradation pathways that control the metabolic turnover of DOC and its accumulation in the deep ocean. However, a multivariate approach is required to constrain current carbon fluxes so that we may better predict how the cycling of oceanic DOC will be altered with continued climate change. Ocean warming, acidification, and oxygen depletion may upset the balance between the primary production and heterotrophic reworking of DOC, thus modifying the amount and/or composition of recalcitrant DOC. Climate change and anthropogenic activities may enhance mobilization of terrestrial DOC and/or stimulate DOC production in coastal waters, but it is unclear how this would affect the flux of DOC to the open ocean. Here, we assess current knowledge on the oceanic DOC cycle and identify research gaps that must be addressed to successfully implement its use in global scale carbon models.

Description: This work was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) project number 422798570. The Hanse-Wissenschaftskolleg and the Geochemical Society provided funding for the conference. Additional support was provided by the National Science Foundation OCE #1756812 to SW. TB acknowledges funding from ETH Zürich and JAMSTEC. JM was supported by the Netherlands Earth System Science Centre. SP-G was funded by COPAS Sur-Austral (CONICYT PIA APOYO CCTE AFB170006). GG-S acknowledges funding from DFG, DI 842/6-1.