Search

The distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs) in soils has been shown to correlate with pH and mean annual air temperature. Because of this dependence brGDGTs have found an application as palaeoclimate proxies in coastal marine sediments, based on the assumption that their distribution is not altered during the transport from soils to marine systems by rivers. To study the processes acting on the brGDGT distributions, we analysed the full suite of brGDGTs, including the recently described 6-Me brGDGTs, in both the suspended particulate matter (SPM) of the Siberian Yenisei River and the SPM and sediments of its outflow in the Kara Sea. The brGDGT distribution in the SPM of the Yenisei River was fairly constant and characterized by high abundances of the 6-Me brGDGTs, reflecting their production at the neutral pH of the river water. However, the brGDGT distribution showed marked shifts in the marine system. Firstly, in the Yenisei River Mouth, the fractional abundance of the 6-Me brGDGTs decreases sharply. The brGDGT signature in the Yenisei River Mouth possibly reflects brGDGTs delivered during the spring floods that may carry a different distribution. Also, coastal cliffs were shown to contain brGDGTs and to influence especially those sites without major river inputs (e.g. Khalmyer Bay). Further removed from the river mouth, in-situ production of brGDGTs in the marine system influences the distribution. However, also the fractional abundance of the tetramethylated brGDGT Ia increases, resulting in a distribution that is distinct from in-situ produced signals at similar latitudes (Svalbard). We suggest that this shift may be caused by preferential degradation of labile (riverine in-situ produced) brGDGTs and the subsequent enrichment in less labile (soil) material. The offshore distribution indeed agrees with the brGDGT distribution encountered in a lowland peat. This implies that the offshore Kara Sea sediments possibly carry a soil-dominated signal, indicating potential for palaeoclimate reconstructions at this site. Both in the river system and coastal cliffs, brGDGTs were much more abundant than crenarchaeol, an archaeal isoprenoid GDGT, resulting in high (>0.93) Branched and Isoprenoid Tetraether (BIT) index values. Moving downstream in the marine sediments, a decrease in brGDGT concentrations, coeval with an increase in crenarchaeol, resulted in decreasing BIT index values. This decrease correlates with changes in bulk proxies for terrigenous input (δ13Corg, C/N), confirming the use of the BIT index to trace the delivery of river-transported and coastal cliff-derived terrigenous organic matter.

International audience; A new archaeal lipid biomarker, C 20,25 sn-2, C-7 hydroxy isoprenoid glycerol diether, has been identified in methane-related carbonates from six methane seep locations. The molecular structure resembles that of sn-2 hydroxyarchaeol but the hydroxy group-bearing moiety at the sn-2 position comprises a regular C 25 instead of a C 20 isoprenoid chain. Compound specific stable carbon isotope measurements revealed δ 13C values ranging from -96‰ to -129‰, which are similar to δ 13C values of sn-2 hydroxyarchaeol. This supports the origin of the novel compound from archaea involved in the anaerobic oxidation of methane. It also suggests a common source, i.e. archaea within the ANME-2 group, which is consistent with the previously reported 16S rDNA data for the same samples. The frequent appearance of the novel sn-2 isoprenoidal hydroxy glycerol diether in cold seepage sediments with high salinity environments, and its distinct structural similarities with membrane lipids of halophilic and methanogenic microbes, suggests that ANME-2 methanotrophic archaea thriving at elevated salinity are the possible biological source for this specific lipid.

Carbonate chimneys and other carbonate structures occur widespread in the Gulf of Cadiz and probably reflect the presence of cold seeps and associated release of methane in the geological past, possibly in the Early Pleistocene, but it is unclear under what conditions and by which processes these carbonates were formed. We studied a fossil methane-related carbonate crust collected from the Kidd mud volcano in the gulf. Concentrations of microbial lipids, their stable carbon isotope composition, sequences of fossil 16S rRNA genes of anaerobic methanotrophic archaea in combination with mineralogical and carbon and oxygen isotopic composition of carbonate were obtained for seven different horizons of the crust. This combination of organic and inorganic geochemical techniques with molecular ecological methods gave a consistent view on processes resulting in the formation of the crust and indicated that it took place in two phases and in a downward direction. Archaeal lipid biomarkers and fossil 16S rRNA gene sequence data revealed the dominance of archaeal ANME-2 group and elevated methane partial pressures during the formation of the top part of the crust. The lower part of the carbonate was likely formed in an environment with reduced methane fluxes as revealed by the dominance of fossil remains of ANME-1 archaea. The combination of these methods can be used as an effective tool to reconstruct in unprecedented detail the palaeo-biogeochemical processes resulting in the formation of carbonate fabrics. This interdisciplinary strategy may also be applied for other fossil methane-derived carbonates, generating new concepts and knowledge about past methane-related carbonate systems.

This study evaluates the glycerol dialkyl glycerol tetraether (GDGT) distribution and provenance in sediments (spanning a minimum of 13.3 ka) from the St. Anna Trough (Northern Kara Sea). The site has experienced extensive fluctuation in the delivery of river-derived organic matter (OM), caused by a eustatic change in sea level. This is in line with the record of the concentration of the isoprenoid GDGT, crenarchaeol, produced by marine Thaumarchaota, which was low at the bottom of the core, increasing gradually in the most shallow unit. The concentration of branched (br)GDGTs showed an opposite trend and a marked shift in distribution. The deepest sediments (> 10 ka), with a distribution currently encountered in surface sediments in front of the Yenisei River, are characterized by terrigenous brGDGTs, whereas the distribution in the shallowest unit (< 10 ka) is strongly influenced by marine, in-situ brGDGTs. During the shift from terrigenous to marine-sourced brGDGTs, there was one horizon where a pronounced shift in the brGDGT distribution was observed and the brGDGT concentration significantly decreased. As the brGDGTs delivered to the current Kara Sea system are derived from several sources, we postulate that a temporary change in the relative importance of the brGDGT sources happened during this interval. Both in-situ production and changing brGDGT provenance have implications for paleoclimate reconstruction using brGDGTs. In-situ production of marine brGDGTs results in a higher reconstructed pH. However, these in-situ produced brGDGTs did not influence the reconstructed mean annual air temperature (MAT), when the MATmrs calibration was used. Changes in the relative contribution of brGDGT sub-pools were shown, however, to influence both soil pH reconstruction and MAT reconstruction.

Bacteriohopanepolyols (BHPs) are ubiquitous bacterial membrane lipids, encountered in soils, river and marine suspended particulate matter (SPM) and sediments. Their abundance and distribution provides a direct means to identify bacterial inputs and can be used to trace soil-derived bacterial organic matter (OM) and in some cases the presence of bacterial groups and their activities in aquatic systems. We have studied the BHP distribution in the SPM of a major Siberian River (Yenisei River) that crosses a large latitudinal gradient, draining a large part of Mongolia and Siberian Russia. The Yenisei River is the main river to flow into the Kara Sea, a shelf sea of the Arctic Ocean. We show that the BHP distribution and concentration of SPM and surface sediments of the Yenisei Outflow in the Kara Sea allow to trace soil-marker BHPs and evaluate the performance of the R′soil index, a proxy developed to trace bacterial soil-derived OM. Soil-marker BHPs are present in the Yenisei River, and their concentration decreases from the Yenisei River Outflow into the offshore marine sediments. The R′soil correlates well with an independent proxy for bacterial OM, the BIT-index (r2 = 0.82) and has a moderate correlation with the δ13Corg values, a bulk OM proxy for terrigenous input (r2 = 0.44). Consequently, the R′soil index performs well in the Kara Sea, strengthening its application for tracing bacterial OM in the Arctic Ocean, both in modern and downcore sediments. Furthermore, a suite of BHPs that are characteristic for methanotrophic bacteria, i.e. 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol) and 35-aminobacteriohopane-31,32,33,34-tetrol (aminotetrol), is encountered in the Yenisei Outflow sediments. These components are partly sourced from terrigenous sources, but are likely also produced in-situ in the marine sediments. The distribution of the pentafunctionalized cyclitol ether BHP in the marine systems is noteworthy, and indicates that it can possibly be applied as a marker for cyanobacterial biomass in marine sediments.

Mud volcanoes (MVs) are formed by expulsion due to lateral or vertical compression of overpressured fluids in the sub-surface. Their sediments are characterized by a specific lithology called mud breccia, which is composed of inorganic and organic matter sourced from different sedimentary units and transported from the sub-surface to the seafloor. Biomarker lipid distributions were determined for sediment cores collected from the Kazakov, NIOZ and Odessa MVs in the Sorokin Trough, northeastern Black Sea. This revealed different mud breccia sources that are directly linked to the location of the fracture zones or diapiric folds formed by tectonic compression. The Kazakov MV shows biomarker characteristics of relatively mature organic matter, likely related to the Maycopian Shale Formation. The NIOZ and Odessa MVs contain immature organic matter derived from much shallower sediments overpressed by rising Maycopian diapirs. In the mud breccia from the NIOZ MV, biomarkers clearly record two different mud eruption episodes reflected in distinct distributions from unrelated sedimentary facies. Hence, the study shows that, although the organic matter of a mud breccia is sourced from a complex mixture of lithofacies, the collective biomarker signal reveals specific signatures of the sedimentary sections that contributed most to the migrated fluid.

During TTR11 Cruise (2001), three areas of active fluid venting and mud volcanism were investigated in the Black Sea below the oxic zone at depths varying between 800 and 2200 m. Authigenic carbonates often associated with microbial mats were recovered from the sea floor and the shallow subsurface. Structural and petrographic observations allowed the distinction of five different types of authigenic carbonates; three of these consist of carbonate-cemented layered hemipelagic sedimentary units, while the other two consist of carbonate-cemented mud breccia sediment and authigenic micrite slabs. The carbonate cements consist predominantly of micritic Mg calcite. Their d 13 CCaCO3 varies between 8.5x and 46.9x at the different sampling locations,indicatingthatauthigenic carbonatesincorporate variableproportions ofcarbonderivedfromthe anaerobicoxidationof methane (AOM), the oxidation of organic matter and from sea water. Methane is the dominant component among other hydrocarbon gases in these sediments. Its relative amount varies from 99.9% to 95.1% of total hydrocarbon gases and its d 13 C values range fromi40xtoi74x. Methane in sediments associated with the carbonate crusts shows carbon isotopic values 25–30x lighter than the authigenic carbonates at all the studied sites, indicating that methane present in the seeping fluids confers a distinct isotopic signature to the carbonate deposits at each location. Models proposed for the formation of carbonate slabs in the subsurface imply methane seepage impeded by homogenous clayey laminae or by pre-existing slabs, coupled with microbial activity oxidising methane and organic matter present in the sediment. Mud breccia crust pavements on the sea floor form by carbonate cementation of methane-charged sediment. Gas saturation of the sediment is confirmed by the presence of gas hydrates, whose shape indicates an association with authigenic carbonates, supporting the idea that sedimentary structures can control gas distribution.

International audience; Here we present a case study of three cold-water coral mounds in a juvenile growth stage on top of the Pen Duick Escarpment in the Gulf of Cadiz; Alpha, Beta and Gamma mounds. Although cold-water corals are a common feature on the adjacent cliffs, mud volcanoes and open slope, no actual living cold-water coral has been observed. This multidisciplinary and integrated study comprises geophysical, sedimentological and (bio)geochemical data and aims to present a holistic view on the interaction of both environmental and geological drivers in cold-water coral mound development in the Gulf of Cadiz. Coring data evidences (past or present) methane seepage near the Pen Duick Escarpment. Several sources and pathways are proposed, among which a stratigraphic migration through uplifted Miocene series underneath the escarpment. The dominant morphology of the escarpment has influenced the local hydrodynamics within the course of the Pliocene, as documented by the emplacement of a sediment drift. Predominantly during post-Middle Pleistocene glacial episodes, favourable conditions were present for mound growth. An additional advantage for mound formation near the top of Pen Duick Escarpment is presented by seepage-related carbonate crusts which might have offered a suitable substrate for coral settling. The spatially and temporally variable character and burial stage of the observed open reef frameworks, formed by cold-water coral rubble, provides a possible model for the transition from cold-water coral reef patches towards juvenile mound. These rubble “graveyards” not only act as sediment trap but also as micro-habitat for a wide range of organisms. The presence of a fluctuating Sulphate–Methane Transition Zone has an important effect on early diagenetic processes, affecting both geochemical and physical characteristics, transforming the buried reef into a solid mound. Nevertheless, the responsible seepage fluxes seem to be locally variable. As such, the origin and evolution of the cold-water coral mounds on top of the Pen Duick Escarpment is, probably more than any other NE Atlantic cold-water coral mound province, located on the crossroads of environmental (hydrodynamic) and geological (seepage) pathways.

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are bacterial membrane lipids found in several environments, including soils, rivers and lakes, whose distribution varies with temperature and pH, although this dependence is apparently not the same for the different environments. Mixing of brGDGT sources may thus complicate palaeoenvironmental reconstruction. The extent to which brGDGTs in a lake outflow reflect the distribution delivered by upstream rivers was studied for Lake Baikal (Russia), one of the largest freshwater lakes worldwide. Fifteen brGDGTs in suspended particulate matter (SPM) of the Selenga River and its outflow from the lake were quantified. The river and lake SPM had rather different distributions. The riverine distribution was still apparent in the SPM of the lake surface water 5 km from the river mouth, but shifts in the distribution were already apparent in the SPM of the surface water after 1 km. Based on the brGDGT distributions of the SPM of the Selenga outflow and that of the lake, conservative mixing between the river and the lake brGDGT distributions could not fully explain the observed shifts in distributions. Both preferential degradation and in situ production of brGDGTs in the surface and, especially, bottom water of the river outflow were potentially responsible. This implies that a riverine lipid distribution delivered to a lake can be modified prior to being transported downstream. The lacustrine brGDGT distribution, that possibly could have reflected a mixture of mountainous and Selenga River SPM, was not recognized in downstream Yenisei River SPM. The watershed of Lake Baikal thus does not seem to contribute to the brGDGTs transported to the marine system. As many large rivers have major lakes in their watershed, this has implications for palaeoclimate reconstruction from river fan sediments globally.

A Siberian peat contains a high abundance of three unknown isomers of hexamethylated branched (br) GDGTs, of which two are present as a second peak eluting shortly after the known hexamethyl br GDGT containing two 5,13,16-trimethyloctacosanyl moieties. Tandem high performance liquid chromatography–mass spectrometry (HPLC–MS2) did not reveal substantial differences in the MS2 spectrum of the two peaks. HPLC isolation of the two peaks of the hexamethylated br GDGT followed by ether cleavage and GC–MS characterization of the hydrocarbons formed, using supersonic molecular beam (SMB) ionization, revealed the second peak to be composed mainly of a novel hexamethyl br GDGT, possessing two 6,13,16-trimethyloctacosanyl moieties. In addition, both chromatographically separated hexamethylated br GDGTs contained a smaller quantity (20–33%) of a non-symmetrical isomer, with one 13,16-dimethyloctacosanyl and one tetramethyloctacosanyl (either 5,13,16,24- or 6,13,16,23-) moiety. Hexamethylated br GDGTs thus consist of four structural isomers. Furthermore, the pentamethylated br GDGT was also isolated and shown to contain both 5,13,16- and 6,13,16-trimethyloctacosanyl moieties, so is composed of two structural isomers. The assignments reveal why environmental distributions of br GDGTs are sometimes complex, which may have implications for the use of br GDGTs in palaeoclimate reconstruction.

We report on a multidisciplinary study of cold seeps explored in the Central Nile deep-sea fan of the Egyptian margin. Our approach combines in situ seafloor observation, geophysics, sedimentological data, measurement of bottom-water methane anomalies, pore-water and sediment geochemistry, and Th-230/U dating of authigenic carbonates. Two areas were investigated, which correspond to different sedimentary provinces. The lower slope, at similar to 2100 m water depth, indicates deformation of sediments by gravitational processes, exhibiting slope-parallel elongated ridges and seafloor depressions. In contrast, the middle slope, at similar to 1650 m water depth, exhibits a series of debris-flow deposits not remobilized by post-depositional gravity processes. Significant differences exist between fluid-escape structures from the two studied areas. At the lower slope, methane anomalies were detected in bottom-waters above the depressions, whereas the adjacent ridges show a frequent coverage of fractured carbonate pavements associated with chemosynthetic vent communities. Carbonate U/Th age dates (similar to 8 kyr BP), pore-water sulphate and solid phase sediment data suggest that seepage activity at those carbonate ridges has decreased over the recent past. In contrast, large (similar to 1 km(2)) carbonate-paved areas were discovered in the middle slope, with U/Th isotope evidence for ongoing carbonate precipitation during the Late Holocene (since similar to 5 kyr BP at least). Our results suggest that fluid venting is closely related to sediment deformation in the Central Nile margin. It is proposed that slope instability leads to focused fluid flow in the lower slope and exposure of 'fossil' carbonate ridges, whereas pervasive diffuse flow prevails at the unfailed middle slope.

Marine Geology, v. 261, n. 1-4, p. 138-152, 2009. http://dx.doi.org/10.1016/j.margeo.2009.02.005; International audience; This paper reports the first "in situ" seafloor observations of fluid escape structures in a fault-controlled caldera-type depression of about 8 km diameter, named the Menes caldera, in the Eastern Mediterranean sea off Egypt (western province of the Nile Deep Sea Fan). A detailed analysis of seven Nautile dives, performed during the Nautinil cruise in 2003, focused on determining the nature, origin, importance, mechanisms and environmental impacts of the fluid escape processes from the geological observations. Seafloor maps, constructed from direct visual observations and video records made from the submersible, and sampling results, for three mud volcanoes of the caldera, Cheops, Chephren and Mykerinos show differences in activity but many common characteristics. The three volcanoes show a crater-like depression. The study reveals a strong contrast between Mykerinos, where no seepage activity was found, and the craters of Cheops and Chephren, where an intense activity of brine seepage was discovered. On Cheops, a dome of dark grey mud raises slightly above the brine surface in the central part of the brine lake, and shows numerous circular vents of 1-2 m diameter that become gradually colonized by microbial mats. Chephren hosts a deep (> 200 m) and warm (45 °C) brine lake. Alternations of areas void of or covered with microbial mats at the surface of the Chephren brine lake indicate large surface disturbances that may result from the occurrence of several active vents at the bottom of the lake. A special feature at Chephren is a brine overflow at the western edge of the crater, also indicative of the very high activity of brine seepage. The Nautinil observations indicate that the Menes caldera in the Eastern Mediterranean is a highly active site of brine seepage. Growth faults rooted in pre-Messinian sediment layers provide pathways for warm fluids to escape pressurized source levels below the Messinian salt.

The Eastern Mediterranean hosts a variety of active cold seep systems, such as gas chimneys, mud volcanoes and pockmarks, in water depths of 500 to 3200 m. As part of the NAUTINIL expedition in 2003, the sediments of cold seeps on the Nile Deep Sea Fan (NDSF) were sampled for the first time for biogeochemical and microbiological analyses. Here we compare rates of the anaerobic oxidation of methane (AOM) and sulfate reduction (SR) as well as the microbial community structure of a variety of cold seep systems including mud volcanoes, pockmarks and brine seeps. Our results revealed strong differences in microbial activity among the different seep systems of the Eastern, Central and Western provinces of the NDSF, as well as the Olimpi field (Central Mediterranean Ridge). Integrated over a sediment depth of 10 cm below the seafloor, SR rates ranged from 0.1–66 mmol m− 2 d− 1 and AOM rates from 0.1–3.6 mmol m− 2 d− 1. SR was often considerably higher than methane oxidation, indicating that electron donors other than methane were utilized. In general, the lowest rates were associated with pockmarks and carbonate pavements, and highest rates with bacterial mats above the gassy sediments of mud volcano centers. 16S rRNA gene analysis and fluorescence in situ hybridization (FISH), revealed the presence of all known groups of marine methane oxidizing Archaea (i.e. ANME-1, -2, -3) and also of methane oxidizing Bacteria (i.e. Methylobacter sp. and relatives) in some seep sediments. Presumably syntrophic sulfate-reducing bacterial partners of ANMEs were also detected in association with the ANMEs. Several ANMEs formed consortia with unknown bacterial partners. The microbial community structure reflected the presence of typical seep microorganisms at all sites investigated, but differed to varying extents between the different types of seeps. Despite the high availability of methane and sulfate, methanotrophic microbial activity and biomass were lower at the seeps of the Eastern Mediterranean compared to those of other continental margins for unknown reasons.

We investigated lipid biomarkers in three depth-intervals of a methane-derived carbonate crust collected from a pockmark in the Nile Deep-Sea fan sampled during the Nautinil cruise of the R/V l'Atalante . A diverse set of 13 C-depleted archaeal and bacterial lipids were detected along this crust with δ 13 C values as low as − 118‰. This provides evidence that anaerobic oxidation of methane was the main process that induced the formation of this carbonate crust. Archaeal lipid biomarker distributions revealed the presence of archaea belonging both to the ANME-1 and ANME-2 phylogenetic clusters, with the former predominating. The distribution and compound specific δ 13 C values of AOM-derived lipid biomarkers showed no significant variations with depth. These results infer that the archaeal community structure and thus the local seepage environment remained relatively stable during the 5000 kyr period of the carbonate crust precipitation.

Soil-derived branched glycerol dialkyl glycerol tetraethers (brGDGTs) in marine river fan sediments have a potential use for determining changes in the mean annual temperature (MAT) and pH of the river watershed soils. Prior to their incorporation in marine sediments, the compounds are transported to the marine system by rivers. However, emerging evidence suggests that the brGDGTs in freshwater systems can be derived from both soil run-off and in situ production. The production of brGDGTs in the river system can complicate the interpretation of the brGDGT signal delivered to the marine system. Therefore, we studied the distribution of brGDGT lipids in suspended particulate matter (SPM) of the Yenisei River. Chromatographic improvements allowed quantification of the recently described hexamethylated brGDGT isomer, characterized by having two methyl groups at the 6/6 ' instead of the 5/5 ' positions, in an environmental dataset for the first time. This novel compound was the most abundant brGDGT in SPM from the Yenisei. Its fractional abundance correlated well with that of the 6-methyl isomer of the hexamethylated brGDGT that contains one cyclopentane moiety. The Yenisei River watershed is characterized by large differences in MAT (>11 degrees C) as it spans a large latitudinal range (46-73 degrees N), which would be expected to be reflected in brGDGT distributions of its soils. However, the brGDGT distributions in its SPM show little variation. Furthermore, the reconstructed pH values are high compared to the watershed soil pH. We, therefore, hypothesize that the brGDGTs in the Yenisei River SPM are predominantly produced in situ and not primarily derived from erosion of soil. This accounts for the absence of a change in the temperature signal, as the river water temperature is more stable. Using a lake calibration, the reconstructed temperature values agree with the mean summer temperatures (MST) recorded. The brGDGTs delivered to the sea by the Yenisei River during this season are thus not soil-derived, possibly complicating the use of brGDGTs in marine sediments for palaeoclimate reconstructions.

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are bacterial membrane lipids that occur ubiquitously in soils and lacustrine sediments and have great potential as proxy indicators for paleotemperature and pH reconstructions. Initially, brGDGTs in lakes were thought to originate from soils of the watershed. The composition of the lacustrine brGDGT pool, however, often differs substantially from that in catchment soils, complicating the application of the brGDGT paleothermometer to lake sediments. This suggests that terrigenous brGDGT signals in lacustrine sedimentary archives may be affected by aquatic in situ production. In sediments of a Swiss mountain lake, we detected a novel hexamethylated brGDGT, which elutes between the known 5- and 6-methyl brGDGT isomers during HPLC–MS analysis. This novel isomer accounted for 8.5% of the total brGDGTs. Most remarkably, this brGDGT was not detected in soils collected from the catchment of the lake, providing circumstantial evidence for an in situ brGDGT source in the lake’s water column or sediments. Isolation of the compound by preparative HPLC and subsequent GC–MS analysis of the alkyl chains revealed that the novel brGDGT comprises two structural isomers. One possesses a 5,13,16- and a 6,13,16-trimethyloctacosanyl moiety and constitutes 84% of the new brGDGT; the second contains a 13,16-dimethyloctacosanyl and a 5,13,16,23-tetramethyloctacosanyl moiety. The δ13C values of both the alkyl chains derived from the novel brGDGT (−46‰) and all other major brGDGTs (−43‰ to −44‰) were significantly lower than those of brGDGT-derived alkanes in catchment soils (−27‰ to −28‰) further attesting to in situ production of brGDGTs in the studied lake.