Bulk and molecular proxies of sediment core GeoB6518-1

A 20 kyr long sediment sequence from the Congo deep sea fan (core GeoB 6518-1), one of the world's largest deep sea river fans, has been analysed for bulk and molecular proxies in order to reconstruct the marine, soil and plant organic carbon (OC) contributions to these sediments since the last glacial maximum. The bulk proxies applied, C/N ratio and d13Corg, ranged from 10 to 12.5 and from -24.5 to -21 per mill VPDB, respectively. As molecular proxies, concentrations of marine derived alkenones and terrestrial derived odd-numbered n-alkanes were used, which varied between 0.2 and 4 µg/g dry weight sediment. In addition, the branched vs. isoprenoid tetraether (BIT) index, a proxy for soil organic matter input, was used, which varied from 0.3 to 0.5 in this core. Application of binary mixing models, based on the different individual proxies, showed estimates for terrestrial OC input varying by up to 50% due to the heterogeneous nature of the OC. Application of a three end-member mixing model using the d13Corg content, the C/N ratio and the BIT index, enabled the distinction of soil and plant organic matter as separate contributors to the sedimentary OC pool. The results show that marine OC accounts for 20% to 40% of the total OC present in the deep sea fan sediments over the last 20 kyr and that soil OC accounts for about half (45% on average) of the OC present. This suggests that soil OC represents the majority of the terrestrial OC delivered to the fan sediments. Accumulation rates of the plant and soil OC fractions over the last 20 kyr varied by a factor of up to 5, and are strongly related to sediment accumulation rates. They showed an increase starting at ca. 17 kyr BP, a decline during the Younger Dryas, peak values during the early Holocene and lower values in the late Holocene. This pattern matches with reconstructions of past central African humidity and Congo River discharge from the same core and revealed that central African precipitation patterns exert a dominant control on terrestrial OC deposition in the Congo deep sea fan. Marine OC accumulation rates are only weakly related to sediment accumulation rates and vary only little over time compared to the terrigenous fractions. These variations are likely a result of enhanced preservation during times of higher sedimentation rates and of relative small fluctuations in primary production due to wind-driven upwelling.

Sedimentary n-alkanes, their hydrogen isotopes, GDGTs and d15N as well as d13Corg of lake Nam Co, Tibet

The transition from the last Glacial to the current Interglacial, the Holocene, represents an important period with climatic and environmental changes impacting ecosystems. In this study, we examined the interplay between the Indian Ocean Summer Monsoon (IOSM) and the Westerlies at lake Nam Co, southern Tibet to understand the climatic effects on the ecosystem. Different organic geochemical proxies (n-alkanes, glycerol dialkyl glycerol tetraethers, dD, d13Corg, d15N) are applied to reconstruct the environmental and hydrological changes on one of the longest available paleorecords at the Tibetan Plateau. Based on our paleohydrological dD proxies, the aquatic signal lags the terrestrial one due to specific ecological thresholds, which, in addition to climatic changes, can influence aquatic organisms. The aquatic organisms' response strongly depends on temperature and associated lake size, as well as pH and nutrient availability. Because the terrestrial vegetation reacts faster and more sensitively to changes in the monsoonal and climatic system, the dD of n-C29 and the reconstructed inflow water signal represent an appropriate IOSM proxy. In general, the interplay of the different air masses seems to be primarily controlled by solar insolation. In the Holocene, the high insolation generates a large land-ocean pressure gradient associated with strong monsoonal winds and the strongest IOSM. In the last glacial period, however, the weak insolation promoted the Westerlies, thereby increasing their influence at the Tibetan Plateau. Our results help to elucidate the variable IOSM, and they illustrate a remarkable shift in the lake system regarding pH, d13Corg and d15N from the last glacial to the Holocene interglacial period.

Biphytane and stable carbon isotopic values of sugars and glycerol from ODP Hole 204-1245D and 201-1229A

The membrane lipids diglycosyl-glycerol dibiphytanyl glycerol tetraethers (2G-GDGTs) in marine subsurface sediments are believed to originate from uncultivated benthic archaea, yet the production of 2G-GDGTs from subseafloor samples has not been demonstrated in vitro. In order to validate sedimentary biosynthesis of 2G-GDGTs, we performed a stable carbon isotope probing experiment on a subseafloor sample with six different 13C-labelled substrates (bicarbonate, methane, acetate, leucine, glucose and Spirulina platensis biomass). After 468 days of anoxic incubation, only glucose and S. platensis resulted in label uptake in lipid moieties of 2G-GDGTs, indicating incorporation of carbon from these organic substrates. The hydrophobic moieties of 2G-GDGTs showed minimal label incorporation, with up to 4 per mil 13C enrichment detected in crenarchaeol-derived tricyclic biphytane from the S. platensis-supplemented slurries. The 2G-GDGT-derived glucose or glycerol moieties also showed 13C incorporation (Dd13C = 18 - 38 per mil) in the incubations with glucose or S. platensis, consistent with a lipid salvage mechanism utilized by marine benthic archaea to produce new 2G-GDGTs. The production rates were nevertheless rather slow, even when labile organic matter was supplied. The 2G-GDGT turnover times of 1700 - 20 500 years were much longer than those estimated for subseafloor microbial communities, implying that sedimentary 2G-GDGTs as biomarkers of benthic archaea are cumulative records of past and present generations.

Stable isotope and geochemical record of sediments from the Bering Sea

here is controversy over the role of marine methane hydrates in atmospheric methane concentrations and climate change during the last glacial period. In this study of two sediment cores from the southeast Bering Sea (700 m and 1467 m water depth), we identify multiple episodes during the last glacial period of intense methane flux reaching the seafloor. Within the uncertainty of the radiocarbon age model, the episodes are contemporaneous in the two cores and have similar timing and duration as Dansgaard-Oeschger events. The episodes are marked by horizons of sediment containing 13C-depleted authigenic carbonate minerals; 13C-depleted archaeal and bacterial lipids, which resemble those found in ANME-1 type anaerobic methane oxidizing microbial consortia; and changes in the abundance and species distribution of benthic foraminifera. The similar timing and isotopic composition of the authigenic carbonates in the two cores is consistent with a region-wide increase in the upward flux of methane bearing fluids. This study is the first observation outside Santa Barbara Basin of pervasive, repeated methane flux in glacial sediments. However, contrary to the "Clathrate Gun Hypothesis" (Kennett et al., 2003), these coring sites are too deep for methane hydrate destabilization to be the cause, implying that a much larger part of the ocean's sedimentary methane may participate in climate or carbon cycle feedback at millennial timescales. We speculate that pulses of methane in these opal-rich sediments could be caused by the sudden release of overpressure in pore fluids that builds up gradually with silica diagenesis. The release could be triggered by seismic shaking on the Aleutian subduction zone caused by hydrostatic pressure increase associated with sea level rise at the start of interstadials.

(Table 1) Ratio of hydroxy-GDGT vs. the total core GDGT was calculated based on the detection of hydroxy-GDGT

Hydroxylated glycerol dialkyl glycerol tetraethers (hydroxy-GDGTs) were detected in marine sediments of diverse depositional regimes and ages. Mass spectrometric evidence, complemented by information gleaned from two-dimensional (2D) 1H-13C nuclear magnetic resonance (NMR) spectroscopy on minute quantities of target analyte isolated from marine sediment, allowed us to identify one major compound as a monohydroxy-GDGT with acyclic biphytanyl moieties (OH-GDGT-0). NMR spectroscopic and mass spectrometric data indicate the presence of a tertiary hydroxyl group suggesting the compounds are the tetraether analogues of the widespread hydroxylated archaeol derivatives that have received great attention in geochemical studies of the last two decades. Three other related compounds were assigned as acyclic dihydroxy-GDGT (2OH-GDGT-0) and monohydroxy-GDGT with one (OH-GDGT-1) and two cyclopentane rings (OH-GDGT-2). Based on the identification of hydroxy-GDGT core lipids, a group of previously reported unknown intact polar lipids (IPLs), including the ubiquitously distributed H341-GDGT (Lipp J. S. and Hinrichs K. -U. (2009) Structural diversity and fate of intact polar lipids in marine sediments. Geochim. Cosmochim. Acta 73, 6816-6833), and its analogues were tentatively identified as glycosidic hydroxy-GDGTs. In addition to marine sediments, we also detected hydroxy-GDGTs in a culture of Methanothermococcus thermolithotrophicus. Given the previous finding of the putative polar precursor H341-GDGT in the planktonic marine crenarchaeon Nitrosopumilus maritimus, these compounds are synthesized by representatives of both cren- and euryarchaeota. The ubiquitous distribution and apparent substantial abundance of hydroxy-GDGT core lipids in marine sediments (up to 8% of total isoprenoid core GDGTs) point to their potential as proxies.

Isotopic signature of specific biomarkers derived from anaerobic methanotrophic archaea (ANME groups) and sulphate-reducing bacteria (SRB) at different cold seep provinces

Anaerobic methane-oxidizing microbial communities in sediments at cold methane seeps are important factors in controlling methane emission to the ocean and atmosphere. Here, we investigated the distribution and carbon isotopic signature of specific biomarkers derived from anaerobic methanotrophic archaea (ANME groups) and sulphate-reducing bacteria (SRB) responsible for the anaerobic oxidation of methane (AOM) at different cold seep provinces of Hydrate Ridge, Cascadia margin. The special focus was on their relation to in situ cell abundances and methane turnover. In general, maxima in biomarker abundances and minima in carbon isotope signatures correlated with maxima in AOM and sulphate reduction as well as with consortium biomass. We found ANME-2a/DSS aggregates associated with high abundances of sn-2,3-di-O-isoprenoidal glycerol ethers (archaeol, sn-2-hydroxyarchaeol) and specific bacterial fatty acids (C16:1omega5c, cyC17:0omega5,6) as well as with high methane fluxes (Beggiatoa site). The low to medium flux site (Calyptogena field) was dominated by ANME-2c/DSS aggregates and contained less of both compound classes but more of AOM-related glycerol dialkyl glycerol tetraethers (GDGTs). ANME-1 archaea dominated deeper sediment horizons at the Calyptogena field where sn-1,2-di-O-alkyl glycerol ethers (DAGEs), archaeol, methyl-branched fatty acids (ai-C15:0, i-C16:0, ai-C17:0), and diagnostic GDGTs were prevailing. AOM-specific bacterial and archaeal biomarkers in these sediment strata generally revealed very similar d13C-values of around -100 per mill. In ANME-2-dominated sediment sections, archaeal biomarkers were even more 13C-depleted (down to -120 per mill), whereas bacterial biomarkers were found to be likewise 13C-depleted as in ANME-1-dominated sediment layers (d13C: -100 per mill). The zero flux site (Acharax field), containing only a few numbers of ANME-2/DSS aggregates, however, provided no specific biomarker pattern. Deeper sediment sections (below 20 cm sediment depth) from Beggiatoa covered areas which included solid layers of methane gas hydrates contained ANME-2/DSS typical biomarkers showing subsurface peaks combined with negative shifts in carbon isotopic compositions. The maxima were detected just above the hydrate layers, indicating that methane stored in the hydrates may be available for the microbial community. The observed variations in biomarker abundances and 13C-depletions are indicative of multiple environmental and physiological factors selecting for different AOM consortia (ANME-2a/DSS, ANME-2c/DSS, ANME-1) along horizontal and vertical gradients of cold seep settings.

Organic geochemistry of sediments from North Alex Mud Vulcano

Hydrocarbon seeps are ubiquitous at gas-prone Cenozoic deltas such as the Nile Deep Sea Fan (NDSF) where seepage into the bottom water has been observed at several mud volcanoes (MVs) including North Alex MV (NAMV). 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 d13C ~-46.6 per mil VPDB and dD ~-228 per mil 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 d13C-CH4 ~-60 per mil 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.

Element concentration and GDGT fractional abundances of sediment core GeoB3910-2

In dieser Arbeit wurde das Zeitintervall zwischen 20 und 10 ka vor heute einschließlich des Heinrichevent 1 und der Younger Dryas am Kern GeoB 3910-2 neu untersucht. An organischen Parametern, basierend auf der Verteilung von bakteriellen GDGTs, und Elementkonzentrationen wurde eine Rekonstruktion der klimatischen Bedingungen und Veränderungen im Hinterland von NO Brasilien durchgeführt. Es zeigt sich, dass sich die durchschnittliche Landtemperatur gleich der Oberflächenwassertemperatur verhält und im Gegensatz zu den Phasen von H6 bis H2 dem antarktischen Erwärmungstrend ab 17 ka vor heute folgt. Weiterhin konnte gezeigt werden, dass durch die südwärts Verlagerung der ITCZ während H1 und der YD die Niederschläge in NO Brasilen intensiviert wurden, was eine Ausbreitung der Flüsse und Änderung der Erosionsgebiete zur Folge hatte.

Fractional abundance and indices for brGDGTs and crenarchaeol in dust samples, surface water samples and surface sediment samples

Branched glycerol dialkyl glycerol tetraethers (brGDGTs) are membrane lipids produced by soil bacteria and occur in near coastal marine sediments as a result of soil organic matter input. Their abundance relative to marine-derived crenarchaeol, quantified in the BIT index, generally decreases offshore. However, in distal marine sediments, low relative amounts of brGDGTs can often still be observed. Sedimentary in situ production as well as dust input have been suggested as potential, though as yet not well constrained, sources. In this study brGDGT distributions in dust were examined and compared with those in distal marine sediments. Dust was sampled along the equatorial West African coast and brGDGTs were detected in most of the samples, albeit in low abundance. Their degree of methylation and cyclisation, expressed in the MBT' (methylation index of branched tetraethers) and DC (degree of cyclisation) indices, respectively, were comparable with those for African soils, their presumed source. Comparison of DC index values for brGDGTS in global soils, Congo deep-sea river fan sediments and dust with those of distal marine sediments clearly showed, however, that distal marine sediments had significantly higher values. This distinctive distribution is suggestive of sedimentary in situ production as a source of brGDGTs in marine sediments, rather than dust input. The presence of in situ produced brGDGTs in marine sediments means that caution should be exercised when applying the MBT'-CBT palaeothermometer to sediments with low BIT index values, i.e. < 0.1, based on our dataset.

Stable carbon isotope compositions and concentrations of biphytanes from IODP Hole 311-U1327C and 311-U1328B

We have investigated the distributions and carbon isotopic compositions of archaeal membrane lipids in gas-hydrate-bearing sediments collected from the northern Cascadia Margin offshore from Vancouver Island (Sites U1327 and U1328) by the R/V JOIDES Resolution during IODP Expedition 311. Archaeal lipid biomarkers, including glycerol dialkyl glycerol tetraethers (GDGTs), tend to become abundant below 100 mbsf (meters below sea floor). Tricyclic biphytane (BP[3]; which is a robust biomarker derived from GDGT), crenarchaeol, and other BPs exhibit d13C values of ca. -20 per mil, and become abundant between 130 and 230 mbsf at Site U1328. In this depth range, concentrations of ammonium and phosphate in interstitial waters also increase, suggesting that a larger population and higher activity of heterotrophic community consisting of crenarchaeota and other archaea decompose the sedimentary organic matter, thereby liberating ammonium and phosphate. Such crenarchaeotic activity can produce other metabolic products such as molecular hydrogen by fermentation of organic matter during diagenesis. Furthermore, near the organic matter decomposition zone (130 to 230 mbsf), a probable methanogen biomarker (13C-depleted BP[1] with d13C values as low as -48.8 per mil) becomes abundant, indicating that methanogens utilize these diagenetic products. The molecular and isotopic distributions of archaeal lipid biomarkers indicate that the archaeal community plays an important role in the biogeochemical cycles of deep-sea sediments, including both methanogenesis and nutrient recycling.