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.

Fatty acids and intact polar lipids of laminated microbial sediments from St. Peter Ording, German Wadden Sea

Hidden for the untrained eye through a thin layer of sand, laminated microbial sediments occur in supratidal beaches along the North Sea coast. The inhabiting microbial communities organize themselves in response to vertical gradients of light, oxygen or sulfur compounds. We performed a fine-scale investigation on the vertical zonation of the microbial communities using a lipid biomarker approach, and assessed the biogeochemical processes using a combination of microsensor measurements and a 13C-labeling experiment. Lipid biomarker fingerprinting showed the overarching importance of cyanobacteria and diatoms in these systems, and heterocyst glycolipids revealed the presence of diazotrophic cyanobacteria even in 9 to 20 mm depth. High abundance of ornithine lipids (OL) throughout the system may derive from sulfate reducing bacteria, while a characteristic OL profile between 5 and 8 mm may indicate presence of purple non-sulfur bacteria. The fate of 13C-labeled bicarbonate was followed by experimentally investigating the uptake into microbial lipids, revealing an overarching importance of cyanobacteria for carbon fixation. However, in deeper layers, uptake into purple sulfur bacteria was evident, and a close microbial coupling could be shown by uptake of label into lipids of sulfate reducing bacteria in the deepest layer. Microsensor measurements in sediment cores collected at a later time point revealed the same general pattern as the biomarker analysis and the labeling experiments. Oxygen and pH-microsensor profiles showed active photosynthesis in the top layer. The sulfide that diffuses from deeper down and decreases just below the layer of active oxygenic photosynthesis indicates the presence of sulfur bacteria, like anoxygenic phototrophs that use sulfide instead of water for photosynthesis.

Chemical characterization and quantification of the brown algal storage compound laminarin

In search of a meaningful stress indicator for Fucus vesiculosus we found that the often used quantitative determination procedures for the polysaccharide laminarin (beta-1,3-glucan) result in different kind of problems, uncertainties and limitations. This chemical long-term storage form of carbon enables perennial brown algae in seasonally fluctuating ecosystems to uncouple growth from photosynthesis. Because of this high ecological relevance a reliable and precise method for determination and quantification of laminarin is needed. Therefore, a simple, cold water extraction method coupled to a new quantitative liquid chromatography-mass spectrometrical method (LC-MS) was developed. Laminarin was determined in nine out of twelve brown algal species, and its expected typical molar mass distribution of 2000-7000 Da was confirmed. Furthermore, laminarin consisted of a complex mixture of different chemical forms, since fifteen chemical laminarin species with distinct molecular weights were measured in nine species of brown algae. Laminarin concentrations in the algal tissues ranged from 0.03 to 0.86% dry weight (DW). The direct chemical characterization and quantification of laminarin by LC-MS represents a powerful method to verify the biochemical and ecological importance of laminarin for brown algae. Single individuals of Laminaria hyperborea, L. digitata, Saccharina latissima, F. serratus, F. vesiculosus, F. spiralis, Himanthalia elongata, Cystoseira tamariscifolia, Pelvetia canaliculata, Ascophyllum nodosum, Halidrys siliquosa and Dictyota dichotoma were collected in fall (18.11.2013) during spring low tide from the shore of Finavarra, Co. Clare, west coast of Ireland (53° 09' 25'' N, 09° 06' 58'' W). After sampling, the different algae were immediately transported to the lab, lyophilized and sent to the University of Rostock. Laminarin was extracted with cold ultrapure water from the algal samples. Before extraction they were ground to < 1 mm grain size with an analytical mill (Ika MF 10 Basic). The algal material (approx. 1.5 g DW) was extracted in ultrapure water (8 mL) on a shaker (250 rpm) for 5 h. After the addition of surplus ultrapure water (4 mL) and shaking manually, 1 mL of the sample was filter centrifuged (45 µm) at 14,000 rpm (Hettich Mikro 22 R). The slightly viscous supernatant was free of suspended material and converted into a microvial (300 µL) for further analysis. The extracts were analyzed using liquid chromatography-mass spectrometry (LC-MS) analysis (LTQ Velos Pro ion trap spectrometer with Accela HPLC, Thermo Scientific). Laminarin species were separated on a KinetexTM column (2.6 µm C18, 150 x 3 mm). The mobile phase was 90 % ultrapure water and 10 % acetonitrile, run isocratically at a flow rate of 0.2 mL min-1. MS was working in ESI negative ion mode in a mass range of 100 - 4000 amu. Glucose contents were determined after extraction using high-performance liquid chromatography (HPLC). Extracted samples were analyzed in an HPLC (SmartLine, Knauer GmbH) equipped with a SUPELCOGELTM Ca column (30 x 7,8 mm without preColumn) and RI-detector (S2300 PDA S2800). Water was used as eluent at a flow rate of 0.8 mL min-1 at 75 °C. Glucose was quantified by comparison of the retention time and peak area with standard solutions using ChromGate software. Mannitol was extracted from three subsamples of 10-20 mg powdered alga material (L. hyperborea, L. digitata, S. latissima, F. serratus, F. vesiculosus, F. spiralis, H. elongata, P. canaliculata, A. nodosum, H. siliquosa) and quantified, following the HPLC method described by Karsten et al. (1991). For analyzing carbon and nitrogen contents, dried algal material was ground to powder and three subsamples of 2 mg from each alga thalli were loaded and packed into tin cartridges (6×6×12 mm). The packages were combusted at 950 °C and the absolute contents of C and N were automatically quantified in an elemental analyzer (Elementar Vario EL III, Germany) using acetanilide as standard according to Verardo et al. (1990).

(Table 1) Composition of paraffin hydrocarbons at DSDP Site 56-434

Geochemical investigation of 18 samples of sediments from Site 434 involved determining the content of organic carbon, of bitumoid A (The chloroform A-chl and alcohol-benzene A-alb extracts) and its various fractions, and of individual hydrocarbons as well as the structural group composition of resins. We identified certain samples that differed sharply from the rest by their increased bitumen content and relatively low molecular hydrocarbons and by the fact that their resinous components were more neutral and aliphatic in composition. The distribution of bitumoid and its components seems to reflect migration processes in operation during the early stages of the transformation of organic matter.

Studies of the microbial diversity on analyzed samples from from Peru Margin, Equatorial Pacific, Hydrate Ridge, and Juan de Fuca Ridge

Marine sediments harbor an enormous quantity of microorganisms, including a multitude of novel species. The habitable zone of the marine sediment column begins at the sediment-water interface and probably extends to depths of several thousands of meters. Studies of the microbial diversity in this ecosystem have mostly relied on molecular biological techniques. We used a complementary method - analysis of intact polar membrane lipids - to characterize the in-situ microbial community in sediments covering a wide range of environmental conditions from Peru Margin, Equatorial Pacific, Hydrate Ridge, and Juan de Fuca Ridge. Bacterial and eukaryotic phospholipids were only detected in surface sediments from the Peru Margin. In contrast, deeply buried sediments, independent of their geographic location, were dominated by archaeal diether and tetraether lipids with various polar head groups and core lipids. We compared ring distributions of archaeal tetraether lipids derived from polar glycosidic precursors with those that are present as core lipids. The distributions of these related compound pools were distinct, suggestive of different archaeal sources, i.e., the polar compounds derive from sedimentary communities and the core lipids are fossil remnants from planktonic communities with possible admixtures of decayed sedimentary archaea. This in-situ production of distinct archaeal lipid populations potentially affects applications of the TEX86 paleotemperature proxy as demonstrated by offsets in reconstructed temperatures between both pools. We evaluated how varying cell and lipid stabilities will influence the sedimentary pool by using a box-model. The results are consistent with (i) a requirement of continuous inputs of freshly synthesized lipids in subsurface sediments for explaining the observed distribution of intact polar lipids, and (ii) decreasing lipid inputs with increasing burial depth.

Lipids and polycyclic aromatic hydrocarbons in bottom sediments from the Atlantic sector of the Southern Ocean

Distribution and composition of lipids and contents of alkanes and polycyclic aromatic hydrocarbons(PAHs) in bottom sediments of the Scotia and Weddell seas are discussed. Comparatively low concentrations of organic carbon (average 0.35%) and lipids (average 0.024%) result from rapid decomposition of organic matter in upper layers of the water column. Composition of alkanes indicates that lipids are of autochthonous origin, and stable concentrations of PAHs (average 25.8 ppb, sigma 15.3 ppb) indicate that they represent the background level for bottom sediments. Higher concentrations of PAHs in sediments near the King George Island (252.1 ppb) and different distributions of individual polyarenes are produced there by the heating systems of the Polish Antarctic Station.

Geochemistry of Eocene sediments from ODP Site 171-1052 on the Black Nose, Atlantic Ocean

We use an X-ray fluorescence (XRF) Core Scanner to obtain records of elemental concentrations in sediment cores from Ocean Drilling Program (ODP) Leg 171B, Site 1052 (Blake Nose, Atlantic margin of northern Florida).This record spans the Middle to Late Eocene, as indicated by bio- and magnetostratigraphy, and displays cyclicity that can be attributed to the orbital forcing of a combination of climate, ocean circulation, or productivity. We use the XRF counts of iron and calcium as a proxy of the relative contribution from calcium carbonate and terrestrial material to construct a new composite depth record. This new composite depth record provides the basis to extend the astronomically calibrated geological time scale into the Middle Eocene and results in revised estimates for the age and duration of magnetochrons C16 through C18. In addition, we find an apparent change in the dominance of orbitally driven changes in obliquity and climatic precession at around 36.7 Ma on our new time scale. Long term amplitude modulation patterns of eccentricity and obliquity in the data do not seem to match the current astronomical model any more, suggesting the possibility of new constraints on astronomical calculations.

Hydrocarbons in surface layer bottom sediments from the North Dvina Riverand the southern part of the Dvina Bay, White Sea

Analysis of molecular composition of alkanes in bottom sediments of the southern part of Dvina Bay (White Sea) in October 2001 revealed the following main peculiarities of hydrocarbon behavior in the estuary: dominating of high molecular C23-C45 compounds and irregular distribution of hydrocarbons in bottom sediments as a result of high sedimentation rate and active hydrodynamics in the studied area.

Fatty acids, alcohols and hydrocarbons of microbial mats from Lake 2A on Kiritimati Island

Modern microbial mats are widely recognized as useful analogs for the study of biogeochemical processes relevant to paleoenvironmental reconstruction in the Precambrian. We combined microscopic observations and investigations of biomarker composition to investigate community structure and function in the upper layers of a thick phototrophic microbial mat system from a hypersaline lake on Kiritimati (Christmas Island) in the Northern Line Islands, Republic of Kiribati. In particular, an exploratory incubation experiment with 13C-labeled bicarbonate was conducted to pinpoint biomarkers from organisms actively fixing carbon. A high relative abundance of the cyanobacterial taxa Aphanocapsa and Aphanothece was revealed by microscopic observation, and cyanobacterial fatty acids and hydrocarbons showed 13C-uptake in the labeling experiment. Microscopic observations also revealed purple sulfur bacteria (PSB) in the deeper layers. A cyclic C19:0 fatty acid and farnesol were attributed to this group that was also actively fixing carbon. Background isotopic values indicate Calvin-Benson cycle-based autotrophy for cycC19:0 and farnesol-producing PSBs. Biomarkers from sulfate-reducing bacteria (SRB) in the top layer of the mat and their 13C-uptake patterns indicated a close coupling between SRBs and cyanobacteria. Archaeol, possibly from methanogens, was detected in all layers and was especially abundant near the surface where it contained substantial amounts of 13C-label. Intact glycosidic tetraether lipids detected in the deepest layer indicated other archaea. Large amounts of ornithine and betaine bearing intact polar lipids could be an indicator of a phosphate-limited ecosystem, where organisms that are able to substitute these for phospholipids may have a competitive advantage.

Sedimentary lipids and palynomorphs of sediment core ABC26 from the Eastern Mediterranean

Selective degradation of organic matter in sediments is important for reconstructing past environments and understanding the carbon cycle. Here, we report on compositional changes between and within lipid classes and kerogen types (represented by palynomorph groups) in relation to the organic matter flux to the sea floor and oxidation state of the sediments since the early Holocene for central Eastern Mediterranean site ABC26. This includes the initially oxic but nowadays anoxic presapropelic interval, the still unoxidised lower part of the organic rich S1 sapropel, its postdepositionally oxidised and nowadays organic-poor upper part as well as the overlying postsapropelic sediments which have always been oxic. A general ~ 2.3 times increase in terrestrial and marine input during sapropel formation is estimated on the basis of the total organic carbon (TOC), pollen, spore, dinoflagellate cyst, n-alkane, n-alkanol and n-alkanoic acid concentration changes in the unoxidised part of the sapropel. The long-chain alkenones, 1,15 diols and keto-ols, loliolides and sterols indicate that some plankton groups, notably dinoflagellates, may have increased much more. Apart from the terrestrial and surface water contributions to the sedimentary organic matter, anomalous distributions and preservation of some C23-C27 alkanes, alkanols and alkanoic acids have been observed, which are interpreted as a contribution by organisms living in situ. Comparison of the unoxidised S1 sapropel with the overlying oxidised sapropel and the organic matter concentration profiles in the oxidised postsapropelic sediments demonstrates strong and highly selective aerobic degradation of lipids and palynomorphs. There seems to be a fundamental difference in degradation kinetics between lipids and pollen which may be possibly related with the absence of sorptive preservation as a protective mechanism for palynomorph degradation. The n-alkanes, Impagidinium, and Nematosphaeropsis are clearly more resistant than TOC. The n-alkanols and n-carboxylic acids are about equally resistant whereas the pollen, all other dinoflagellate cysts and other lipids appear to degrade considerably faster, which questions the practice of normalising to TOC without taking diagenesis into account. Selective degradation also modifies the relative distributions within lipid classes, whereby the longer-chain alkanes, alcohols and fatty acids disappear faster than their shorter-chain equivalents. Accordingly, interpretation of lipid and palynomorph assemblages in terms of pre- or syndepositional environmental change should be done carefully when proper knowledge of the postdepositional preservation history is absent. Two lipid-based preservation proxies are tested the diol-keto-ol oxidation index based on the 1,15C30 diol and keto-ols (DOXI) and the alcohol preservation index (API) whereby the former seems to be the most promising.

Composition of bottom sediments from the Isfjord, Western Svalbard

Lithology, heavy mineral associations, and chemical composition of bottom sediments studied in two gravity cores from Isfjord, Western Spitsbergen (Svalbard) accompanied by high-frequency seismic records, provide a new insight on provenance and glaciomarine sedimentation in the fjord from the last deglaciation through Holocene.

Abundances and d13C values of n-alkanes extracted from sediment samples of ODP Hole 116-717C

Siwalik paleosol and Bengal Fan sediment samples were analyzed for the abundance and isotopic composition of n-alkanes in order to test for molecular evidence of the expansion of C4 grasslands on the Indian subcontinent. The carbon isotopic compositions of high-molecular-weight alkanes in both the ancient soils and sediments record a shift from low d13C values (ca. -30 per mil) to higher values (ca. -22 per mil) prior to 6 Ma. This shift is similar in magnitude to that recorded by paleosol carbonate and fossil teeth, and is consistent with a relatively rapid transition from dominantly C3 vegetation to an ecosystem dominated by C4 plants typical of semi-arid grasslands. The n-alkane values from our paleosol samples indicate that the isotopic change began as early as 9 Ma, reflecting either a growing contribution of C4 plants to a dominantly C3 biomass or a decrease in water availability to C3 plants. Molecular and isotopic analyses of other compounds, including n-alcohols and low-molecular weight n-alkanes indicate paleosol organic matter contains contributions from a mixture of sources, including vascular plants, algae and/or cyanobacteria and microorganisms. A range of inputs is likewise reflected in the isotopic composition of the total organic carbon from these samples. In addition, the n-alkanes from two samples show little evidence for pedegenic inputs and we suggest the compounds were derived instead from the paleosol's parent materials. We suggest the record of vegetation in ancient terrestrial ecosystems is better reconstructed using isotopic signatures of molecular markers, rather than bulk organic carbon. This approach provides a means of expanding the spatial and temporal records of C4 plant biomass which will help to resolve possible tectonic, climatic or biological controls on the rise of this important component of the terrestrial biosphere.

Lithology and organic geochemistry at DSDP Hole 77-535

Analyses of extractable organic matter from selected core samples obtained at DSDP Site 535 in the eastern Gulf of Mexico show that the asphalt (or tar) and adjacent oil stains in Lower Cretaceous fractured limestones have a common origin and are not derived from the surrounding organic-matter-rich limestones. Organic matter indigenous to those surrounding limestones was shown to be thermally immature and incapable of yielding the hydrocarbon mixture discovered. In contrast, the oil-stained and asphaltic material appears to be a post-migration alteration product of a mature oil that has migrated from source rocks deeper in the section, or from stratigraphically equivalent but compositionally different source-facies down-dip from the drill site. Further, hydrocarbons of the altered petroleum residues were shown to be similar to Sunniland-type oils found in Lower Cretaceous rocks of South Florida. The results suggest that shallowwater, platform-type source-rock facies similar to those that generated Sunniland-type oils, or deeper-water facies having comparable oil-generating material, are present in this deep-water (> 3000 m) environment. These findings have important implications for the petroleum potential in the eastern Gulf of Mexico and for certain types of deep-sea sediments.