Organic carbon chemistry of late Tertiary to Quaternary sediments ODP Leg 107

We analyzed samples from ODP Holes 652A and 654A (Leg 107, Tyrrhenian Sea) for the amount, type, and thermal maturity of organic matter. The sediments encompass clastic and biogenic lithologies, which were deposited on the passive margin east of Sardinia since the late Miocene to the Pleistocene. Marine, hypersaline/evaporitic, lacustrine/riverine, and finally hemipelagic marine conditions with occasional anoxic(?) interludes gave rise to very diverse sedimentary facies. The majority of samples is lean in organic matter (<0.2% TOC). Notable exceptions are Tortonian sediments (TOC average 0.3%), Messinian oil shales from Core 107-652A-64R (up to 11% TOC), Messinian lacustrine/fluvial sediments from Hole 652A (TOC average 0.42%,), and Pleistocene sapropel samples (>2% TOC). The Messinian oil shale in Hole 652A appears to be the only mature hydrocarbon source rock. In general, Pliocene sediments are the leanest and least mature samples. Pleistocene and Pliocene samples derive organic matter from a marine source. In spite of obvious facies differences in the Messinian between the two sites, pyrolysis results are not conclusive in separating hypersaline facies of Site 654 from the fresh water facies of Site 652, because both appear to have received terrestrial organic tissue as the main component of TOC. It is apparent from the distribution of maximum pyrolysis temperatures that heat flow must have been considerably higher at Site 652 on the lower margin in the Messinian. Molecular maturity indices in lipid extracts substantiate the finding that the organic matter in Tortonian and Messinian samples from Hole 654A is immature, while thermal maturation is more advanced in coeval samples from Hole 652A. Analyses of lipid biomarkers showed that original odd-even predominance was preserved in alkanes and alkylcyclohexanes from Messinian samples in Hole 654A, while thermal maturation had removed any odd-even predominance in Hole 652A. Isomerization data of hopanes and steranes support these differences in thermal history for the two sites. Hopanoid distribution further suggests that petroleum impregnation from a deeper, more mature source resulted in the co-occurrence of immature and mature groups of pentacyclic biomarkers. Even though the presence of 4-methylsteranes may imply that dinoflagellates were a major source for organic matter in the oil shale interval of Hole 652, we did not find intact dinoflagellates or related nonskeletal algae during microscopic investigation of the organic matter in the fine laminations. Morphologically, the laminations resemble bacterial mats.

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.

Ladderane lipid analysis and pore water and sediment chemistry of sediment cores from the continental shelf and slope off northwest Africa

The presence and abundance of anaerobic ammonium-oxidizing (anammox) bacteria was investigated in continental shelf and slope sediments (300-3000 m water depth) off northwest Africa in a combined approach applying quantitative polymerase chain reaction (q-PCR) analysis of anammox-specific 16S rRNA genes and anammox-specific ladderane biomarker lipids. We used the presence of an intact ladderane monoether lipid with a phosphocholine (PC) headgroup as a direct indicator for living anammox bacteria and compared it with the abundance of ladderane core lipids derived from both living and dead bacterial biomass. All investigated sediments contained ladderane lipids, both intact and core lipids, in agreement with the presence of anammoxspecific 16S rRNA gene copies, indicating that anammox occurs at all sites. Concentrations of ladderane core lipids in core top sediments varied between 0.3 and 97 ng g**-1 sediment, with the highest concentrations detected at the sites located on the shelf at shallower water depths between 300 and 500 m. In contrast, the C20 [3]-ladderane monoether-PC lipid was most abundant in a core top sediment from 1500 m water depth. Both anammox-specific 16S rRNA gene copy numbers and the concentration of the C20 [3]-ladderane monoether-PC lipid increased downcore in sediments located at greater water depths, showing highest concentrations of 1.2 x 10**8 copies g**-1 sediment and 30 pg g**-1 sediment, respectively, at the deepest station of 3000 m water depth. This suggests that the relative abundance of anammox bacteria is higher in sediments at intermediate to deep water depths where carbon mineralization rates are lower but where anammox is probably more important than denitrification.

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.

Lipid biomarkers of shelf sediments from upwelling regions off Namibia, Peru, and Chile

Sediments of upwelling regions off Namibia, Peru, and Chile contain dense populations of large nitrate-storing sulfide-oxidizing bacteria, Thiomargarita, Beggiatoa, and Thioploca. Increased contents of monounsaturated C16 and C18 fatty acids have been found at all stations studied, especially when a high density of sulfide oxidizers in the sediments was observed. The distribution of lipid biomarkers attributed to sulfate reducers (10MeC16:0 fatty acid, ai-C15:0 fatty acid, and mono-O-alkyl glycerol ethers) compared to the distribution of sulfide oxidizers indicate a close association between these bacteria. As a consequence, the distributions of sulfate reducers in sediments of Namibia, Peru, and Chile are closely related to differences in the motility of the various sulfide oxidizers at the three study sites. Depth profiles of mono-O-alkyl glycerol ethers have been found to correlate best with the occurrence of large sulfide-oxidizing bacteria. This suggests a particularly close link between mono-O-alkyl glycerol ether-synthesizing sulfate reducers and sulfide oxidizers. The interaction between sulfide-oxidizing bacteria and sulfate-reducing bacteria reveals intense sulfur cycling and degradation of organic matter in different sediment depths.

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.