Elemental and isotope compositions of lipids, kerogens and asphaltenes from samples of DSDP Hole 41-368

The thermal effects of three (one major and two minor) Miocene diabase intrusions on Cretaceous black shales from DSDP site 41-368 have been analyzed. A concentration gradient was observed, especially for the hydrocarbons, decreasing towards the major intrusion and between the three sills. The thermally-altered samples in the proximity of and between the sills contained elemental sulfur and an excess of thermally-derived pristane over phytane. whereas, the unaltered sediments contained no elemental sulfur, and more phytane than pristane. A maximum yield of the extractable hydrocarbons was observed at a depth of 7 m below the major sill. Two classes of molecular markers were present in this bitumen suite. The first was sesqui-, di- and triterpenoids and steranes. which could be correlated with both terrigenous and autochthonous sources. They were geologically mature and showed no significant changes due to the thermal stress. The second class was found in the altered samples, which contained only polynuclear aromatic hydrocarbons with low alkyl substitution and sulfur and oxygen heterocyclic aromatic compounds. These compounds were derived from pyrolytic reactions during the thermal event. Kerogen was isolated from all of these samples, but only traces of humic substances were present. The H/C, N/C, d13C, d34S and dD all exhibit the expected effects of thermal stress. The kerogen becomes more aromatized and richer in 13C, 34S and D in the proximity of and between the sills. Maturation trends were also measured by the vitrinite reflectance and electron spin resonance, where the thermal stress could be correlated with an elevated country rock temperature and an increased degree of aromaticity. The effects of in situ thermal stress on the organic-rich shales resulted in the generation and expulsion of petroliferous material from the vicinity of the sills.

Contents of organic compounds in sediments from DSDP Legs 1 and 4

Fifteen sediment samples were studied from five drill sites recovered by the Glomar Challenger on Legs I and IV in the Gulf of Mexico and western Atlantic. This study concentrated on compounds derived from biogenic precursors, namely: (1) hydrocarbons, (2) fatty acids, (3) pigments and (4) amino acids. Carbon isotope (dC13) data [values <(-26)?, relative to PDB], long-chain n-alkyl hydrocarbons (>>C27) with odd carbon numbered molecules dominating even carbon numbered species, and presence of perylene proved useful as possible indicators for terrigenous contributions to the organic matter in some samples. Apparently land-derived organic matter can be transported for distances over 1000 km into the ocean and their source still recognized. The study was primarily designed to investigate: (i) the sources of the organic matter present in the sediment, (ii) their stability with time of accumulation and (iii) the conditions necessary for in situ formation of new compounds.

Elemental contents, non-carbonate, fatty acids and alcohols analysis from different Holes of IODP Expedition 310

During IODP Expedition 310 (Tahiti Sea Level), drowned Pleistocene-Holocene barrier-reef terraces were drilled on the slope of the volcanic island. The deglacial reef succession typically consists of a coral framework encrusted by coralline algae and later by microbialites; the latter make up < 80% of the rock volume. Lipid biomarkers were analyzed in order to identify organisms involved in reef-microbialite formation at Tahiti, as the genesis of deglacial microbialites and the conditions favoring their formation are not fully understood. Sterols plus saturated and monounsaturated short-chain fatty acids predominantly derived from both marine primary producers (algae) and bacteria comprise 44 wt% of all lipids on average, whereas long-chain fatty acids and long-chain alcohols derived from higher land plants represent an average of only 24 wt%. Bacterially derived mono-O-alkyl glycerol ethers (MAGEs) and branched fatty acids (10-Me-C16:0; iso- and anteiso-C15:0 and -C17:0) are exceptionally abundant in the microbial carbonates (average, 19 wt%) and represent biomarkers of intermediate-to-high specificity for sulfate-reducing bacteria. Both are relatively enriched in 13C compared to eukaryotic lipids. No lipid biomarkers indicative of cyanobacteria were preserved in the microbialites. The abundances of Al, Si, Fe, Mn, Ba, pyroxene, plagioclase, and magnetite reflect strong terrigenous influx with Tahitian basalt as the major source. Chemical weathering of the basalt most likely elevated nutrient levels in the reefs and this fertilization led to an increase in primary production and organic matter formation, boosting heterotrophic sulfate reduction. Based on the observed biomarker patterns, sulfate-reducing bacteria were apparently involved in the formation of microbialites in the coral reefs off Tahiti during the last deglaciation.

Drained thaw-lake basin soil characteristics of cores from Barrow, Alaska

Arctic soils contain a large fraction of Earth's stored carbon. Temperature increases in the Arctic may enhance decomposition of this stored carbon, shifting the role of Arctic soils from a net sink to a new source of atmospheric CO2. Predicting the impact of Arctic warming on soil carbon reserves requires knowledge of the composition of the stored organic matter. Here, we employ solid state 13C nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared-photoacoustic spectroscopy (FTIR-PAS) to investigate the chemical composition of soil organic matter collected from drained thaw-lake basins ranging in age from 0 to 5500 years before present (y BP). The 13C NMR and FTIR-PAS data were largely congruent. Surface horizons contain relatively large amounts of O-alkyl carbon, suggesting that the soil organic matter is rich in labile constituents. Soil organic matter decreases with depth with the relative amounts of O-alkyl carbon decreasing and aromatic carbon increasing. These data indicate that lower horizons are in a more advanced stage of decomposition than upper horizons. Nonetheless, a substantial fraction of carbon in lower horizons, even for ancient thaw-lake basins (2000-5500 y BP), is present as O-alkyl carbon reflecting the preservation of intrinsically labile organic matter constituents. Climate change-induced increases in the depth of the soil active layer are expected to accelerate the depletion of this carbon.

(Table 2) Distribution of alkenone unsaturation index UK37 of the eastern North Atlantic

This paper reports the concentrations and within-class distributions of long-chain alkenones and alkyl alkenoates in the surface waters (0-50 m) of the eastern North Atlantic, and correlates their abundance and distribution with those of source organisms and with water temperature and other environmental variables. We collected these samples of >0.8 µm particulate material from the euphotic zone along the JGOFS 20°W longitude transect, from 61°N to 24°N, during seven cruises of the UK-JGOFS Biogeochemical Ocean Flux Study (BOFS) in 1989-1991; the biogeographical range of our 53 samples extends from the cold (<10°C), nutrient-rich and highly productive subarctic waters of the Iceland Basin to the warm (>25°C) oligotrophic subtropical waters off Africa. Surface water concentrations of total alkenone and alkenoates ranged from <50 ng/l in oligotrophic waters below 40°N to 2000-4500 ng/l in high latitude E. huxleyi blooms, and were well correlated with E. huxleyi cell densities, supporting the assumption that E. huxleyi is the predominant source of these compounds in the present day North Atlantic. The within-class distribution of the C37 and C38 alkenones and C36 alkenoates varied strongly as a function of temperature, and was largely unaffected by nutrient concentration, bloom status and other surface water properties. The biosynthetic response of the source organisms to growth temperature differed between the cold (<16°C) waters above 47°N and the warmer waters to the south. In cold (<16°C) waters above 47°N, the relative amounts of alkenoates and C38 alkenones synthesized was a strong function of growth temperature, while the unsaturation ratio of the alkenones (C37 and C38) was uncorrelated with temperature. Conversely, in warm (>16°C) waters below 47°N, the relative proportions of alkenoates and alkenones synthesized remained constant with increasing temperature while the unsaturation ratios of the C37 and C38 methyl alkenones (Uk37 and Uk38Me, respectively) increased linearly. The fitted regressions of Uk37 and Uk38Me versus temperature for waters >16°C were both highly significant (r**2 > 0.96) and had identical slopes (0.057) that were 50% higher than the slope (0.034) of the temperature calibration of Uk37 reported by Prahl and Wakeham (1987; doi:10.1038/330367a0) over the same temperature range. These observations suggest either a physiological adjustment in biochemical response to growth temperature above a 16-17°C threshold and/or variation between different E. huxleyi strains and/or related species inhabiting the cold and warm water regions of the eastern North Atlantic. Using our North Atlantic data set, we have produced multivariate temperature calibrations incorporating all major features of the alkenone and alkenoate data set. Predicted temperatures using multivariate calibrations are largely unbiased, with a standard error of approximately ±1°C over the entire data range. In contrast, simpler calibration models cannot adequately incorporate regional diversity and nonlinear trends with temperature. Our results indicate that calibrations based upon single variables, such as Uk37, can be strongly biased by unknown systematic errors arising from natural variability in the biosynthetic response of the source organisms to growth temperature. Multivariate temperature calibration can be expected to give more precise estimates of Integrated Production Temperatures (IPT) in the sedimentary record over a wider range of paleoenvironmental conditions, when derived using a calibration data set incorporating a similar range of natural variability in biosynthetic response.

Contaminant concentrations in ivory gull (Pagophila eburnea) eggs from Svalbard and the Russian Arctic (2006-2007)

We found high levels of contaminants, in particular organochlorines, in eggs of the ivory gull Pagophila eburnea, a high Arctic seabird species threatened by climate change and contaminants. An 80% decline in the ivory gull breeding population in the Canadian Arctic the last two decades has been documented. Because of the dependence of the ivory gull on sea ice and its high trophic position, suggested environmental threats are climate change and contaminants. The present study investigated contaminant levels (organochlorines, brominated flame retardants, perfluorinated alkyl substances, and mercury) in ivory gull eggs from four colonies in the Norwegian Svalbard) and Russian Arctic (Franz Josef Land and Severnaya Zemlya). The contaminant levels presented here are among the highest reported in Arctic seabird species, and we identify this as an important stressor in a species already at risk due to environmental change.