n-Alkane, fatty acid and hopanoic acid concentrations of ODP Site 190-1178 samples

Ocean Drilling Program (ODP) Leg 190 was programmed to investigate deformational, diagenetic, and hydrologic processes and their interactions in the Nankai Trough accretionary prism. Site 1178 is the northernmost site in the Muroto Transect. Slope sediments and the underlying landward-dipping reflector zone were successfully cored. Temperature measurements and Cl concentrations in pore water indirectly indicate the presence of gas hydrate between 120 and 400 meters below seafloor (mbsf) at Site 1178, with the highest concentrations between 150 and 200 mbsf (Shipboard Scientific Party, 2001, doi:10.2973/odp.proc.ir.190.109.2001). Sedimentary structures show a broad range of deformation structures rich in fractures, suggesting active fluid circulation in the Nankai Trough prism. One of the objectives of Leg 190 was to clarify the interplay of various fundamental processes taking place in the Nankai Trough accretionary prism. Bacteria or prokaryotes in deep subsurface sediment play an important role for material transformation and circulation in an accretionary prism. Significant amounts of bacteria are detected in many of the samples examined (Shipboard Scientific Party, 2001, doi:10.2973/odp.proc.ir.190.109.2001). The type of organic matter in sediments is an important factor related to bacterial activity. To assist investigations on material circulation in deep subsurface sediments, the samples from Site 1178 were analyzed for geolipids (extractable organic matter). The basic data set is preliminarily compiled in the present report to show the types of organic matter and their concentrations in sediments from Site 1178.

Fatty acid and stable isotope composition of calanoid copepods in the open eastern Atlantic Ocean during POLARSTERN cruise ANT-XXIX/1

The majority of global ocean production and total export production is attributed to oligotrophic oceanic regions due to their vast regional expanse. However, energy transfers, food-web structures and trophic relationships in these areas remain largely unknown. Regional and vertical inter- and intra-specific differences in trophic interactions and dietary preferences of calanoid copepods were investigated in four different regions in the open eastern Atlantic Ocean (38°N to 21°S) in October/November 2012 using a combination of fatty acid (FA) and stable isotope (SI) analyses. Mean carnivory indices (CI) based on FA trophic markers generally agreed with trophic positions (TP) derived from d15N analysis. Most copepods were classified as omnivorous (CI ~0.5, TP 1.8 to ~2.5) or carnivorous (CI >=0.7, TP >=2.9). Herbivorous copepods showed typical CIs of <=0.3. Geographical differences in d15N values of epi- (200-0 m) to mesopelagic (1000-200 m) copepods reflected corresponding spatial differences in baseline d15N of particulate organic matter from the upper 100 m. In contrast, species restricted to lower meso- and bathypelagic (2000-1000 m) layers did not show this regional trend. FA compositions were species-specific without distinct intra-specific vertical or spatial variations. Differences were only observed in the southernmost region influenced by the highly productive Benguela Current. Apparently, food availability and dietary composition were widely homogeneous throughout the oligotrophic oceanic regions of the tropical and subtropical Atlantic. Four major species clusters were identified by principal component analysis based on FA compositions. Vertically migrating species clustered with epi- to mesopelagic, non-migrating species, of which only Neocalanus gracilis was moderately enriched in lipids with 16% of dry mass (DM) and stored wax esters (WE) with 37% of total lipid (TL). All other species of this cluster had low lipid contents (< 10% DM) without WE. Of these, the tropical epipelagic Undinula vulgaris showed highest portions of bacterial markers. Rhincalanus cornutus, R. nasutus and Calanoides carinatus formed three separate clusters with species-specific lipid profiles, high lipid contents (>=41% DM), mainly accumulated as WE (>=79% TL). C. carinatus and R. nasutus were primarily herbivorous with almost no bacterial input. Despite deviating feeding strategies, R. nasutus clustered with deep-dwelling, carnivorous species, which had high amounts of lipids (>=37% DM) and WE (>=54% TL). Tropical and subtropical calanoid copepods exhibited a wide variety of life strategies, characterized by specialized feeding. This allows them, together with vertical habitat partitioning, to maintain high abundance and diversity in tropical oligotrophic open oceans, where they play an essential role in the energy flux and carbon cycling.

Sterol, n-alcohol and n-alkane composition of living fen plants

In groundwater-fed fen peatlands, the surface biomass decays rapidly and, as a result, highly humified peat is formed. A high degree of humification constrains palaeoecological studies because reliable identification of plant remains is hampered. Organic geochemistry techniques as a means of identifying historical plant communities have been successfully applied tobog peat. The method has also been applied to fen peat, but without reference to the composition of fen plants. We have applied selected organic geochemistry methods to determine the composition of the neutral lipid fractions from 12 living fen plants, to investigate the potential for the distributions to characterize and separate different fen plants and plant groups. Our results show correspondence with previous studies, e.g. C23 and C25n-alkanes dominating Sphagnum spp. and C27 to C31 alkanes dominating vascular plants. However, we also found similarities in n-alkane distributions between Sphagnum spp. and the below ground parts of some vascular plants. We tested the efficiency of different n-alkane ratios to separate species and plant groups. The ratios used for bog studies (e.g. n-C23/n-C25 and n-C23/n-C29) did not work as consistently for fen plants. Some differences in sterol distribution were found between vascular plants and mosses; in general vascular plants had a higher concentration of sterols. When distributions of n-alkanes, n-alkane ratios and sterols were all included as variables, redundancy analysis (RDA) separated different plant groups into their own clusters. Our results imply that the pattern for bog biomarkers cannot directly be applied to fen environments. Nevertheless, they encourage further testing to determine whether or not the identification of plant groups, plants or plant parts from highly humified peat is possible by applying fen species-specific biomarker proxies.

Seasonal changes in the D/H ratio of fatty acids of pelagic microorganisms

Culture studies of microorganisms have shown that the hydrogen isotopic composition of fatty acids depends on their metabolism, but there are only few environmental studies available to confirm this observation. Here we studied the seasonal variability of the deuterium/hydrogen (D/H) ratio of fatty acids in the coastal Dutch North Sea and compared this with the diversity of the phyto- and bacterioplankton. Over the year, the stable hydrogen isotopic fractionation factor epsilon between fatty acids and water ranged between -172 per mil and -237 per mil, the algal-derived polyunsaturated fatty acid nC20:5 being the most D-depleted and nC18:0 the least D-depleted fatty acid. The D-depleted nC20:5 is in agreement with culture studies, which indicates that photoautotrophic microorganisms produce fatty acids which are significantly depleted in D relative to water. The epsilon-lipid/water of all fatty acids showed a transient shift towards increased fractionation during the spring phytoplankton bloom, indicated by increasing chlorophyll a concentrations and relative abundance of the nC20:5 PUFA, suggesting increased contributions of photoautotrophy. Time periods with decreased fractionation (less negative epsilon-lipid/water values) can be explained by an increased contribution by heterotrophy to the fatty acid pool. Our results show that the hydrogen isotopic composition of fatty acids is a useful tool to assess the community metabolism of coastal plankton.

Contents and stable carbon isotope compositions of biomarkers indicative for AOM-communities dominated by different ANME groups in two carbonate samples from Hydrate Hole pockmark

Different types of seep carbonates were recovered from the 'Kouilou pockmarks' on the Congo deep-sea fan in approximately 3100 m water depth. The carbonate aggregates are represented by pyritiferous nodules, crusts and slabs, tubes, and filled molds. The latter are interpreted to represent casts of former burrows of bivalves and holothurians. The nodules consisting of high-Mg-calcite apparently formed deeper within the sediments than the predominantly aragonitic crusts and slabs. Nodule formation was caused by anaerobic oxidation of methane dominantly involving archaea of the phylogenetic ANME-1 group, whereas aragonitic crusts resulted from the activity of archaea of the ANME-2 cluster. Evidence for this correlation is based on the distribution of specific biomarkers in the two types of carbonate aggregates, showing higher hydroxyarchaeol to archaeol ratios in the crusts as opposed to nodules. Formation of crusts closer to the seafloor than nodules is indicated by higher carbonate contents of crusts, probably reflecting higher porosities of the host sediment during carbonate formation. This finding is supported by lower d18O values of crusts, agreeing with precipitation from pore waters similar in composition to seawater. The aragonitic mineralogy of the crusts is also in accord with precipitation from sulfate-rich pore waters similar to seawater. Moreover, the interpretation regarding the relative depth of formation of crusts and nodules agrees with the commonly observed pattern that ANME-1 archaea tend to occur deeper in the sediment than members of the ANME-2 group. Methane represents the predominant carbon source of all carbonates (d13C values as low as -58.9 per mil V-PDB) and the encrusted archaeal biomarkers (d13C values as low as -140 per mil V-PDB). Oxygen isotope values of some nodular carbonates, ranging from + 3.9 to + 5.1per mil V-PDB, are too high for precipitation in equilibrium with seawater, probably reflecting the destabilization of gas hydrates, which are particularly abundant at the Kouilou pockmarks.

Alkane and hydrocarbon concentrations of ODP Leg 104 sites

Sedimentary extractable organic matter was analyzed at three ODP Leg 104 sites in the Norwegian Sea. Organic carbon content ranged from less than 0.1% to a maximum of 1.8%. Extractable organic matter content and unresolved complex mixture concentrations were low and randomly distributed. Low levels of aliphatic (branched and normal) and aromatic hydrocarbons were detected in all of the sediments analyzed. Total aliphatic and aromatic hydrocarbon concentrations ranged from 176 to 3,214 and 6 to 820 ppb, respectively. The concentrations of individual aliphatic (n-C15 to n-C32) and aromatic (two- to five-ring) hydrocarbons were generally less than 50 ppb and less than 10 ppb, respectively. No significant trend with sub-bottom depth was observed in either bulk organic matter or individual hydrocarbon concentrations. The predominant source of Cenozoic sedimentary hydrocarbons is concluded to be ice-rafted debris from the adjacent continent. All sites contain a mixture of recycled, mature petroleum-related and terrestrially derived hydrocarbons.

Carbon geochemistry in serpentinites from and beneath the Lost City Hydrothermal Field

The carbon geochemistry of serpentinized peridotites and gabbroic rocks recovered at the Lost City Hydrothermal Field (LCHF) and drilled at IODP Hole 1309D at the central dome of the Atlantis Massif (Mid-Atlantic Ridge, 30°N) was examined to characterize carbon sources and speciation in oceanic basement rocks affected by long-lived hydrothermal alteration. Our study presents new data on the geochemistry of organic carbon in the oceanic lithosphere and provides constraints on the fate of dissolved organic carbon in seawater during serpentinization. The basement rocks of the Atlantis Massif are characterized by total carbon (TC) contents of 59 ppm to 1.6 wt% and 17863_TC values ranging from -28.7? to +2.3?. In contrast, total organic carbon (TOC) concentrations and isotopic compositions are relatively constant (d13C_TOC: -28.9? to -21.5?) and variations in d13CTC reflect mixing of organic carbon with carbonates of marine origin. Saturated hydrocarbons extracted from serpentinites beneath the LCHF consist of n-alkanes ranging from C15 to C30. Longer-chain hydrocarbons (up to C40) are observed in olivine-rich samples from the central dome (IODP Hole 1309D). Occurrences of isoprenoids (pristane, phytane and squalane), polycyclic compounds (hopanes and steranes) and higher relative abundances of n-C16 to n-C20 alkanes in the serpentinites of the southern wall suggest a marine organic input. The vent fluids are characterized by high concentrations of methane and hydrogen, with a putative abiotic origin of hydrocarbons; however, evidence for an inorganic source of n-alkanes in the basement rocks remains equivocal. We propose that high seawater fluxes in the southern part of the Atlantis Massif likely favor the transport and incorporation of marine dissolved organic carbon and overprints possible abiotic geochemical signatures. The presence of pristane, phytane and squalane biomarkers in olivine-rich samples associated with local faults at the central dome implies fracture-controlled seawater circulation deep into the gabbroic core of the massif. Thus, our study indicates that hydrocarbons account for an important proportion of the total carbon stored in the Atlantis Massif basement and suggests that serpentinites may represent an important (as yet unidentified) reservoir for dissolved organic carbon (DOC) from seawater.

(Table 3) Relative content of n-alkane groups in samples from hydrothermal fields of the Mid-Atlantic Ridge

Optimum conditions were selected for chromatographic separation of model mixtures of C12-C40 n-alkanes. For one of samples of hydrothermal deposits extraction conditions of hydrocarbons were studied and a sample preparation procedure was selected. The procedure was proposed to determine n-alkanes in samples of hydrothermal deposits by means of gas chromatography - mass spectrometry (GC-MS). Detection limit for n-alkanes was 3x10**-9 to 10**-8% depending on components. On the basis of the proposed procedure composition of n-alkanes was studied in samples of hydrothermal deposits collected at the Mid-Atlantic Ridge (Broken Spur, Lost City, and Rainbow hydrothermal fields). Analyses showed that samples contained C14-C35 n-alkanes. Concentrations of the n-alkanes were rather low and varied from 0.002 to 0.038 µg/g. Hypotheses concerning genesis of identified n-alkanes were offered.

Stable oxygen isotope composition of the sea water in the Mediterranean Sea

During the cruises No 17 and 22 of the German research vessel "Meteor", 45 water samples were taken at 4 stations in the central part of the Mediterranean Sea. Mass spectrometrical analyses showed that systematic, but time variable changes of the oxygen isotope ratios occur. Deep water samples (T> 500 m) have a ± constant isotopic composition of d18O = +1.79? (SMOW) and a Chlorinity of 21.399?. These data are discussed with respect to paleotemperature determinations.