Moleculare composition of sediments from ODP Hole 116-717C

We describe the molecular composition of a portion of the solvent-soluble organic material (lipid extract), from three organic rich muds (samples 116-717C-22X-1, 80-86 cm, 116-717C-34X-3, 130-135 cm, and 116-717C-55X-1, 65-70 cm). These samples were taken from Hole 717C, located on the Bengal Fan at a position of 0°55.8'S and 81°23.4'E. Both the palaeoenvironmental and digenetic significance of these lipid distributions have been assessed and found to be consistent with their suspected origins, i.e., turbidites from the upper slope of the western Bay of Bengal and the Ganges-Brahmaputra delta.

Transport of Sterols to the Plasma Membrane of Leek Seedlings1

To investigate the intracellular transport of sterols in etiolated leek (Allium porrum L.) seedlings, in vivo pulse-chase experiments with [1-14C]acetate were performed. Then, endoplasmic reticulum-, Golgi-, and plasma membrane (PM)-enriched fractions were prepared and analyzed for the radioactivity incorporated into free sterols. In leek seedlings sterols are present as a mixture in which (24R)-24-ethylcholest-5-en-3β-ol is by far the major compound (around 60%). The other sterols are represented by cholest-5-en-3β-ol, 24-methyl-cholest-5-en-3β-ol, (24S)-24-ethylcholesta-5,22E-dien-3β-ol, and stigmasta-5,24(241)Z-dien-3β-ol. These compounds are shown to reside mainly in the PM. Our results clearly indicate that free sterols are actively transported from the endoplasmic reticulum to the PM during the first 60 min of chase, with kinetics very similar to that of phosphatidylserine. Such a transport was found to be decreased at low temperature (12°C) and following treatment with monensin and brefeldin A. These data are consistent with a membrane-mediated process for the intracellular transport of sterols to the PM, which likely involves the Golgi apparatus.

Organic compounds in surface sediments from the Pakistan continental margin

In order to assess whether the oxygen-minimum zone (OMZ) in the Arabian sea has an effect on the preservation and composition of organic matter in surface sediments we investigated samples from three different transects on the Pakistan continental margin across the OMZ. In addition to determining the total amount of organic carbon (TOC), we analyzed the extractable lipids by gas chromatography, combined gas chromatography/mass spectrometry, and compound-specific stable carbon isotope measurements. The extractable lipids are dominated by marine organic matter as indicated by the abundance of lipids typical of marine biota and by the bulk and molecular isotopic composition. Sediments from within the OMZ are enriched in organic carbon and in several extractable lipids (i.e. phytol, n-alcohols, total sterols, n-C35 alkane) relative to stations above and below this zone. Other lipid concentrations, such as those of total n-fatty acids and total n-alkanes fail to show any relation to the OMZ. Only a weak correlation of TOC with mineral surface area was found in sediments deposited within the OMZ. In contrast, sediments from outside the OMZ do not show any relationship between TOC and surface area. Among the extractable lipids, only the n-alkane concentration is highly correlated with surface area in sediments from the Hab and Makran transects. In sediments from outside the OMZ, the phytol and sterol concentrations are also weakly correlated with mineral surface area. The depositional environment of the Indus Fan offers the best conditions for an enhanced preservation of organic matter. The OMZ, together with the undisturbed sedimentation at moderate rates, seems to be mainly responsible for the high TOC values in this area. Overall, the type of organic matter and its lability toward oxic degradation, the mineral surface area, the mineral composition, and possibly the secondary productivity by (sedimentary) bacteria also appear to have an influence on organic matter accumulation and composition.

(Table 1) Bulk geochemistry of sediment cores KH-79-3_L3 and KH-79-3_C3

The organic and isotopic geochemical study of two sediment cores (KH-79-3, L-3, and KH-79-3, C-3) from the Oki Ridge in the Japan Sea has revealed that total organic carbon (TOC) mass accumulation rates are extremely high in the 12-11 ka (calendar age) interval and TOC in the sections in the 24-17 ka interval is depleted in 13C by 3.5? relative to Holocene sediments. Alkenone sea surface temperature (SST) shows a decrease from 18° to 14°C from 17.5 to 11.6 ka and a sharp increase from 14° to 19°C from 11.6 to 11.1 ka. The SST changes are associated with the inflow of cold seawater with the vertical water mixing and the inflowof warm Tsushima Current into the Japan Sea. The d13C values for both 24-methylcholesta-5,22-dien-3?-ol (diatom marker) and dinosterol (dinoflagellate marker), are at their minimum from 24 to 17 ka, while those for long-chain alkenones are not. The theoretical considerations on d13C for biomarkers suggest low photosynthetic carbon demand of diatoms and dinoflagellates from 24 to 17 ka.

C1-C7 volatile organic compounds in sediments at DSDP Legs 56-57 Holes

Volatile C1-C7 components in sediments were examined for Japan Trench DSDP Sites 438, 439, 435, 440, 434 and 436, proceeding from west to east. Levels of all components are lowest in the highly fractured sediments of Sites 440 and 434. A number of alkenes, furans, and sulfur compounds were detected in concentrations higher than noted in any other DSDP sediments examined to date. The types, amounts, and specificity of occurrence are similar to those for 1-meter gravity cores we have examined which bear a significant biological imprint. Site 436 shows high levels of saturated and aromatic hydrocarbons, as well as olefins, including traces of dimethycyclopentanes and the highest level of cyclohexene detected in any DSDP sediment we have examined to date. The results from Site 436 were unexpected, considering the low organic-carbon content, absence of biogenic methane, and evidence of an aerobic depositional environment at this site.

Lipid biomarkers in surface sediments from an unusual coastal upwelling area from the SW Atlantic Ocean

The coastal upwelling off Cabo Frio (SE Brazilian coast, SEBC) represents an exception to the world`s oceans since the majority of the upwelling areas are located in eastern boundary current systems. Cabo Frio represents an interesting area for investigation due to its tight physical-biological interaction and the importance of the region as a major fishery area in the SEBC. We analyzed a suite of lipid biomarkers to apportion the main sources of organic matter in surface sediments of the continental shelf off Cabo Frio, comparing the area to non-upwelling regions off the SEBC (shelf break off Cabo Frio and continental shelf off Ubatuba). During spring and summer (the upwelling period), diatoms are probably the major sources of polyunsaturated fatty acids (PUFAs) and C-28 sterols in surface sediments from Cabo Frio continental shelf. Sediments sampled in winter showed, in contrast, lower relative abundance of PUFAs and higher stanol/stenol ratio values. In deeper regions off Cabo Frio, elevated concentrations of alkenones, 24-methylcholest-5,22E-dien-3 beta-ol and 24-ethylcholest-5-en-3 beta-ol during the spring may be produced by prymnesiophytes or cryptophytes and cyanobacteria, respectively. In Ubatuba, the C-27 and C-28 sterols are likely derived from omnivorous salps and nanoflagellates. At non-upwelling areas, despite the increase in biomarker concentrations during spring and summer, lower concentrations of PUFAs, phytol and algal sterols than in shelf areas off Cabo Frio suggest the importance of the upwelling system to the rapid transfer of organic carbon to surface sediments. Our results suggest that spatial and temporal variability in organic matter production and deposition merits consideration for constraining the carbon budgets in the coastal region off Cabo Frio. (C) 2008 Elsevier Ltd. All rights reserved.

Biomarkers in turbidites at ODP Sites 157-951 and 157-952

Free and ester-bound lipid biomarkers were analysed in oxidised and unoxidised parts of four distinct turbidites from the Madeira Abyssal Plain (MAP), which contained 1 to 2% organic carbon homogeneously distributed throughout the turbidites at the time they were deposited. These turbidites are well suited to study the effects of oxic degradation on lipid biomarkers without the complicating influence of varying organic matter sources, sedimentation rates, or bioturbation. One sample from the oxidised turbidite was compared with two samples from the unoxidised part of each turbidite. Postdepositional oxic degradation decreased concentrations of biomarkers by several orders of magnitude. The ester-bound lipids were degraded to a far lesser extent than their free counterparts were. The extent of degradation of different compounds differed substantially. Within a specific class of biomarkers, degradation also took place to a different extent, altering their distributions. This study shows that oxic degradation of the organic matter may have a profound effect on the biomarker fingerprint and may result in a severe bias in, for example, the interpretation of organic matter sources and the estimation of the palaeoproductivity of specific groups of phytoplankton.

Geochemistry of ODP Sites 123-765 and 123-766

The sediments of the Argo and Gascoyne abyssal plains are generally lean in organic matter, are immature, and contain hydrocarbons trapped during sediment deposition rather than those generated during sediment catagenesis. TOC concentrations in the Argo Abyssal Plain Cenozoic sediments are 0.5 wt%, and organic matter appears to be from mixed marine and reworked, degraded, organic matter sources, with the latter being contributed by turbidity flows from the nearby continental margin. TOC concentrations within the Cenozoic sediments of the Gascoyne Abyssal Plain are mostly undetectable (<0.1 wt%). Biomarker distributions determined by gas chromatography (GC) and gas chromatography-mass spectrometry (GCMS) indicate that organic matter extracted from the Lower Cretaceous sediments from both sites is predominantly marine with varying contributions from terrestrial organic matter. The specific marine biomarker, 24-n-propylcholestane is in relatively high abundance in all samples. In addition, the relatively high abundance of the 4-methylsteranes with the 23,24-dimethyl side chain (in all samples) indicates significant dinoflagellate contributions and marine organic matter. The ratios of n-C27/n-C17 reflect relative contributions of marine vs. terrestrial organic matter. TOC, while generally low at Argo, is relatively high near the Barremian/Aptian boundary (one sample has a TOC of 5.1 wt%) and the Aptian/Albian boundary (up to 1.3 wt% TOC), and two samples from the Barremian and Aptian sections contain relatively high proportions of terrestrial organic carbon. TOC values in the Lower Cretaceous sediments from Gascoyne Abyssal Plain are low (<0.1 wt%) near the Aptian/Barremian boundary. TOC values are higher in older sediments, with maxima in the upper Barremian (1.02 wt%), the Barremian/Hauterivian (0.6 wt%), and Valanginian (1.8 wt%). Sediments from the upper Barremian contain higher amounts of terrestrial organic carbon than older sediments.

Biomarker records of DSDP Hole 24-231 and terrestrial sediments

ntegrated terrestrial and marine records of northeast African vegetation are needed to provide long high resolution records of environmental variability with established links to specific terrestrial environments. In this study, we compare records of terrestrial vegetation preserved in marine sediments in the Gulf of Aden [Deep Sea Drilling Project (DSDP) Site 231] and an outcrop of lacustrine sediments in the Turkana Basin, Kenya, part of the East African Rift System. We analyzed higher plant biomarkers in sediments from both deposits of known equivalent age, corresponding to a ca. 50-100 ka humid interval prior to the b-Tulu Bor eruption ca. 3.40 Ma, when the Lokochot Lake occupied part of the Turkana Basin. Molecular abundance distributions indicate that long chain n-alkanoic acids in marine sediments are the most reliable proxy for terrestrial vegetation (Carbon Preference Index, CPI = 4.5), with more cautious interpretation needed for n-alkanes and lacustrine archives. Marine sediments record carbon isotopic variability in terrestrial biomarkers of 2-3 per mil, roughly equivalent to 20% variability in the C3/C4 vegetation contribution. The proportion of C4 vegetation apparently increased at times of low terrigenous dust input. Terrestrial sediments reveal much larger (2-10 per mil) shifts in n-alkanoic acid delta13C values. However, molecular abundance and isotopic composition suggest that microbial sources may also contribute fatty acids, contaminating the lacustrine sedimentary record of terrestrial vegetation.

Stable hydrogen isotopic composition (dD) and stable carbon isotopic composition (d13C) of sediment core GeoB9508-5 off Senegal

To reconstruct variability of the West African monsoon and associated vegetation changes on precessional and millennial time scales, we analyzed a marine sediment core from the continental slope off Senegal spanning the past 44,000 years (44 ka). We used the stable hydrogen isotopic composition (dD) of individual terrestrial plant wax n-alkanes as a proxy for past rainfall variability. The abundance and stable carbon isotopic composition (d13C) of the same compounds were analyzed to assess changes in vegetation composition (C3/C4 plants) and density. The dD record reveals two wet periods that coincide with local maximum summer insolation from 38 to 28 ka and 15 to 4 ka and that are separated by a less wet period during minimum summer insolation. Our data indicate that rainfall intensity during the rainy season throughout both wet humid periods was similar, whereas the length of the rainy season was presumably shorter during the last glacial than during the Holocene. Additional dry intervals are identified that coincide with North Atlantic Heinrich stadials and the Younger Dryas interval, indicating that the West African monsoon over tropical northwest Africa is linked to both insolation forcing and high-latitude climate variability. The d13C record indicates that vegetation of the western Sahel was consistently dominated by C4 plants during the past 44 ka, whereas C3-type vegetation increased during the Holocene. Moreover, we observe a gradual ending of the Holocene humid period together with unchanging ratio of C3 to C4 plants, indicating that an abrupt aridification due to vegetation feedbacks is not a general characteristic of this time interval.