Organic geochemistry of ODP Hole 162-985A sediments

Dark, organic-rich sediments were recovered from the lower Miocene section (~16.6 Ma) in Hole 985A in the Norway Basin during Ocean Drilling Program Leg 162. Organic carbon and total sulfur contents of the dark sediments showed a maximum concentration of 5.6 and 26.1 wt%, respectively. Sulfur enrichment in the sediments indicates that these dark layers were formed under anoxic conditions in bottom water. Four dark and eight greenish gray sediment samples, ranging in age from early Miocene to Pleistocene, were analyzed for lipid-class compounds (aliphatic hydrocarbons, fatty alcohols, and sterols) using gas chromatography (GC) and GC/mass spectrometry to better understand the formation processes of the organic-rich dark layers and to reconstruct the paleoenvironmental changes. The molecular distributions of n-alkanes and fatty alcohols indicate that terrigenous organic matter largely contributed to both types of sediments. Significant amounts of hopanoid hydrocarbons, such as diploptene and hop-17(21)-ene, however, were detected characteristically in the dark sediments, which suggests that prokaryotes such as methane-oxidizing bacteria or cyanobacteria may have significantly contributed to the formation of these organic-rich, dark sediments. These results indicate that the bottom waters of the Norway Basin had been subjected to anoxic conditions during the early Miocene.

Benthic anammox and dentrification rates measured in a slurry incubation experiments at four different stations in the Arabian Sea off Pakistan during the METEOR cruise M74/2 in 2007

Vertical distributions of benthic denitrification and anammox rates within the sediment were estimated from slurry incubation experiments. Rates were used to calculate the contribution of anammox and denitrification to the total N-loss. Briefly, MUC sediment cores were sliced in 2 cm intervals and the sediment was diluted and incubated with degassed bottom water in a gas tight bag. After pre-incubating the bags for 2 h, 15N-labeled substrates were injected into the bags and the slurries were thoroughly mixed. Incubations were performed in the dark at in situ temperatures. The N2 isotope ratio (28N2, 29N2, and 30N2) was determined by gas chromatography-isotopic ratio mass spectrometry (VG Optima, Micromass) and calculated according to Kuypers et al. (2005) and Holtappels et al. (2011), respectively.Furthermore, total organic carbon and nitrogen concentrations were measured of core sediment layers corresponding to those used for rate measurements. Concentrations of organic carbon and nitrogen were determined by combustion/gas chromatography (Carlo Erba NA-1500 CNS analyzer) of dried sediment samples after acidification. The same sediment layer were also used to extract nucleic acids. The concentrations of the DNA in the samples were measured spectrophotometrically with a NanoDrop instrument (Thermo Fisher Scientific Inc.). The biomarker functional gene nirS, encoding the cd1-containing nitrite reductase, for both denitrifiers and marine anammox bacteria were quantified with real-time PCR, using the primers cd3aF/R3cd (5'-GTSAACGTSAAGGARACSGG-3' (Michotey et al., 2000)/5'-GASTTCGGRTGSGTCTTGA-3'; Throback et al., 2004) and Scnir372F/Scnir845R (5'-TGTAGCCAGCATTGTAGCGT-3'/5'-TCAAGCCAGACCCATTTGCT-3'; Lam et al., 2009).

C4-C7 alkenones in deep sea sediments

It is believed that C4 to C7 hydrocarbons in petroleum are formed by the cracking of organic matter at depths generally exceeding 1,000 m at temperatures in excess of 50 °C (Cordel, 1972; Dow, 1974; Tissot et al., 1974)). Also, none of the alkanes in the butane-heptane range are formed biologically as far as is known at present. Consequently, it is thought that they do not occur in shallow, Recent sediments. In 1962, I analysed 22 samples of Recent sediments from 7 different environments and verified that these hydrocarbons were not present at the p.p.m. level (Dunton and Hunt, 1962) although traces of a few hydrocarbons such as butane, isobutane, isopentane and n-heptane have been found (Sokolov, 1957; Veber and Turkeltaub, 1958; Erdman et al., 1958; Emery and Hoggan, 1958). No identification of individual hexanes or heptanes has been reported except when there has been clear evidence of seepage from deeper source sediments (McIver, 1973).

Cholesterol and C30 of sediment profile MD90-963

In a deep-sea sediment core recovered from a site lying well above the local lysocline, several organic geochemical proxies, and two different calcite dissolution indicators, are compared in order to evaluate the relationship between calcite dissolution and paleoproductivity over the past three glacial-interglacial cycles. The degree of foraminiferal break-up, and the CaCO3 particle size distribution, both point to significant periods of dissolution every 22 kyr during glacial stages and substages. These dissolution events are concomitant with periods of enhanced primary productivity, as indicated by the abundance of several biomarkers (alkenones, cholesterol, brassicasterol, keto-ol), used here to indicate changes in paleoproductivity. Dissolution fluctuations are highly coherent and in phase with the estimated paleoproductivity variations providing strong evidence that the observed dissolution is due to organic matter remineralization within the sediments rather, than to changes in CO32? concentration in the overlying water column.

Long chain alkyl diol distribution in Arabian Sea surface sediments

Oxygen exposure has a large impact on lipid biomarker preservation in surface sediments and may affect the application of organic proxies used for reconstructing past environmental conditions. To determine its effect on long chain alkyl diol and keto-ol based proxies, the distributions of these lipids was studied in nine surface sediments from the Murray Ridge in the Arabian Sea obtained from varying water depths (900 to 3000 m) but in close lateral proximity and, therefore, likely receiving a similar particle flux. Due to substantial differences in bottom water oxygen concentration (<3 to 77 µmol/L) and sedimentation rate, substantial differences exist in the time the biomarker lipids are exposed to oxygen in the sediment. Long chain alkyl diol and keto-ol concentrations in the surface sediments (0-0.5 cm) decreased progressively with increasing oxygen exposure time, suggesting increased oxic degradation. The 1,15-keto-ol/diol ratio (DOXI) increased slightly with oxygen exposure time as diols had apparently slightly higher degradation rates than keto-ols. The ratio of 1,14- vs. 1,13- or 1,15-diols, used as upwelling proxies, did not show substantial changes. However, the C30 1,15-diol exhibited a slightly higher degradation rate than C28 and C30 1,13-diols, and thus the Long chain Diol Index (LDI), used as sea surface temperature proxy, showed a negative correlation with the maximum residence time in the oxic zone of the sediment, resulting in ca. 2-3.5 °C change, when translated to temperature. The UK'37 index did not show significant changes with increasing oxygen exposure. This suggests that oxic degradation may affect temperature reconstructions using the LDI in oxic settings and where oxygen concentrations have varied substantially over time.