Description of sediments, epoch, calcium carbonate, orgnic carbon, geolipids and mass accumulation rate at DSDP Holes 92-597A, 92-600 and 92-601B

Low concentrations of organic carbon in slowly accumulating sediments from Sites 597, 600, and 601 reflect a history of low marine productivity in the subtropical South Pacific since late Oligocene times. The distributions of n-alkanes, n-alkanoic acids, and n-alkanols provide evidence of the microbial alteration of sediment organic matter. Landderived hydrocarbons, possibly from eolian transport, dominate n-alkane distributions in these samples.

Biomarkers of early Aptian sediments of the Shatsky Rise

This study investigates organic-rich sedimentary sequences deposited during the early Aptian Oceanic Anoxic Event (OAE1a) at Sites 1207 and 1213 on Shatsky Rise (ODP Leg 198) in the west-central Pacific. Biomarker analyses provide evidence of the algal and bacterial origin of organic matter (OM) in these sediments where the abundance of steroidal components, particularly sterenes and sterones, suggests that the OM includes major contributions from eukaryotic sources in an environment characterized by high phytoplankton productivity. The presence of alkenones at Site 1213B is diagnostic of OM derived from representatives of haptophyte algae among the calcareous nannoplankton and their d13C values (average -31.6 per mil) are consistent with those expected during elevated pCO2. The occurrence and prominence of 2b-methylhopanes and 2b-methylhopanones indicates significant contributions to the OM from cyanobacteria, which are also likely contributors of hopanoids based on their d13C compositions. These biomarker data suggest that oceanic conditions, perhaps nitrate- or iron-limited, were conducive to cyanobacteria production during OAE1a, which appears to distinguish this event from other Cretaceous OAE.

Stable carbon isotope ratios of alkane of IODP Hole 302-M0004A

The Palaeocene/Eocene thermal maximum represents a period of rapid, extreme global warming approx ~55 million years ago, superimposed on an already warm world (Zachos et al., 2003, doi:10.1126/science.1090110; Bowen et al., 2004, doi:10.1038/nature03115; Thomas et al., 2002, doi:10.1130/0091-7613(2002)030<1067:WTFFTF>2.0.CO;2). This warming is associated with a severe shoaling of the ocean calcite compensation depth **4 and a >2.5 per mil negative carbon isotope excursion in marine and soil carbonates (Zachos et al., 2003, doi:10.1126/science.1090110; Bowen et al., 2004, doi:10.1038/nature03115; Thomas et al., 2002, doi:10.1130/0091-7613(2002)030<1067:WTFFTF>2.0.CO;2; Zachos et al., doi:10.1126/science.1109004). Together these observations indicate a massive release of 13C-depleted carbon (Zachos et al., doi:10.1126/science.1109004) and greenhouse-gas-induced warming. Recently, sediments were recovered from the central Arctic Ocean (Backman et al., 2006, doi:10.2204/iodp.proc.302.2006), providing the first opportunity to evaluate the environmental response at the North Pole at this time. Here we present stable hydrogen and carbon isotope measurements of terrestrial-plant- and aquatic-derived n-alkanes that record changes in hydrology, including surface water salinity and precipitation, and the global carbon cycle. Hydrogen isotope records are interpreted as documenting decreased rainout during moisture transport from lower latitudes and increased moisture delivery to the Arctic at the onset of the Palaeocene/Eocene thermal maximum, consistent with predictions of poleward storm track migrations during global warming (Backman et al., 2006, doi:10.2204/iodp.proc.302.2006). The terrestrial-plant carbon isotope excursion (about ~4.5 to ~6 per mil) is substantially larger than those of marine carbonates. Previously, this offset was explained by the physiological response of plants to increases in surface humidity (Bowen et al., 2004, doi:10.1038/nature03115). But this mechanism is not an effective explanation in this wet Arctic setting, leading us to hypothesize that the true magnitude of the excursion - and associated carbon input - was greater than originally surmised. Greater carbon release and strong hydrological cycle feedbacks may help explain the maintenance of this unprecedented warmth.of this unprecedented warmth.

Organic matter based proxies from surface sediments along three transects on the Pakistan continental margin

A valid assessment of selective aerobic degradation on organic matter (OM) and its impact on OM-based proxies is vital to produce accurate environmental reconstructions. However, most studies investigating these effects suffer from inherent environmental heterogeneities. In this study, we used surface samples collected along two meter-scale transects and one longer transect in the northeastern Arabian Sea to constrain initial OM heterogeneity, in order to evaluate selective aerobic degradation on temperature, productivity and alteration indices at the sediment-water interface. All of the studied alteration indices, the higher plant alkane index, alcohol preservation index, and diol oxidation index, demonstrated that they are sensitive indicators for changes in the oxygen regime. Several export production indices, a cholesterol-based stanol/stenol index and dinoflagellate lipid- and cyst-based ratios, showed significant (more than 20%) change only over the lateral oxygen gradients. Therefore, these compounds do not exclusively reflect surface water productivity, but are significantly altered after deposition. Two of the proxies, glycerol dibiphytanyl glycerol tetraether-based TEX86 sea surface temperature indices and indices based on phytol, phytane and pristane, did not show any trends related to oxygen. Nevertheless, unrealistic sea surface temperatures were obtained after application of the TEX86, TEX86L, and TEX86H proxies. The phytol-based ratios were likely affected by the sedimentary production of pristane. Our results demonstrate the selective impact of aerobic organic matter degradation on the lipid and palynomorph composition of surface sediments along a short lateral oxygen gradient and suggest that some of the investigated proxies may be useful tracers of changing redox conditions at the sediment-water interface.

Some parameters of distribution of hydrocarbon paraffin fraction in bottom sediments of the Kara Sea and the Yenisey estuary

During Cruise 49 of R/V Dmitry Mendeleev in the Kara Sea (August-September, 1993) chemical-bitumenological studies of bottom sediments were carried out. Hydrocarbons were analyzed by gas-liquid chromatography. It was found on the basis of distribution of n-alkanes and isoprenoids (pristan and phytan) that organic matter is mainly terrigenous consisting of higher plant remains.

(Table 1) Lithological and organic-geochemical compositions of bottom sediments from the Southwestern Indian Ocean (Mozambique Basin)

Geochemical changes in organic matter of bottom sediments from the Mozambique Basin at the river-sea barrier from the mouths of the Zambezi and Limpopo rivers toward the pelagic zone are discussed. Changes in bitumen, hydrolyzable material, humic acids, amino acids, n-alkanes, and polycyclic aromatic compounds resulting from genetic and diagenetic factors are described. This information is significant for paleoceanology reconstructions and for knowing ways of organic matter transformation into fossil forms.

Total organic carbon in surface sediments of the Ob and Yenisei estuaries and adjacent coastal areas, appendix 1

Two main mechanisms are controlling the accumulation of organic matter in the sediments of the Kara Sea. The large rivers Ob and Yenisei supply significant quantities of freshwater onto the shelf (Lisitsyn and Vinogradov, 1995; Bobrovitskaya et al., 1996; Johnson et al., 1997) and deliver terrigenous organie matter and aquatic algae. Additionally, marine organic matter is produced in the water column. In order to distinguish between the different sources of the organic material maceral analysis, organic-geochemical bulk Parameters and biomarkers (short- and long-chain D-alkanes, fatty acids and pigments) were used to determine the quality (marine vs. terrigenous) and quantity of the organic carbon fraction in the surface sediments taken during the 28th cruise of RV Akademik Boris Petrov (Matthiessen and Stepanets, 1998) (Fig. 1). Previous organic-geochemical investigations (i.e., total organic-carbon content (TOC), hydrogen indices (Hl), CIN-ratios) indicate the importance of terrigenous input of organic matter (Galimov et al., 1996; Stein, 1996). Studies of lipid biomarkers in surface sediments in the Ob estuary show also a predominance of terrestrial constituents and an increase in planktonogenic and bacterial lipids further offshore (Belyaeva and Eglinton, 1997). In complex systems such as the Eurasian continental margin characterized by high input of terrestriallaquatic organic matter and strong seasonal variation in sea-ice Cover and primary productivity, the Interpretation of the organic geochemical data is much more complicated and restricted in comparison to similar data Sets from low-latitude open-ocean environments (Fahl and Stein, 1998). Microscopical studies (maceral analysisl palynology), however, allow a direct visual inspection of the particulate organic matter and allow to differentiate particles of different biological sources. Thus, a combination of both methods as shown in this study, yields a more precise identification of organic-carbon sources.

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).

Organic carbon and biomarker record from the Laptev Sea continental margin

In order to understand the processes controlling organic carbon deposition (i.e., primary productivity vs. terrigenous supply) and their paleoceanographic significance, three sediment cores (PS2471, PS2474. and PS2476) from the Laptev Sea continental margin were investigated for their content and composition of organic carbon. The characterization of organic matter indudes the determination of buk parameters (hydrogen index values and C/N ratios) and the analysis of specific biomarkers (n-alaknes, fatty acids, alkenones, and pigments). Total organic carbon (TOC) values vary between 0.3 and 2%. In general, the organic matter from the Laptev Sea continental margin is dominated by terrigenous matter throughout. However. significant amounts of marine organic carbon occur. The turbidites, according to a still preliminary stratigraphy probably deposited during glacial Oxygen Isotope Stages 2 and 4, are characterized by maximum amounts of organic carbon of terrigenous origin. Marine organic carbon appears to show enhanced relative abundances in the Termination I (?) and early Holocene time intervals, as indicated by maximum amounts of short chain n-alkanes, short-chain fatty acids, and alkenones. The increased amounts of faity acids, however, may also have a freshwater origin due to increased river discharge at that time. The occurrence of alkenones is suggested to indicate an intensification of Atlantic water inflow along the Eurasian continental margin starting at that time. Oxygen Isotope Stage l accumutation rates of total organic carhon are 0.3, 0.17, and 0.02 C/cm**2/ky in cores PS2476, PS2474, and PS2471, respectively.

Accumulation of particulate organic carbon at the Eurasian continental margin during late Quaternary times

Data on the amount and composition of organic carbon were determined in sediment cores from the Kara and Laptev Sea continental margin, representing oxygen isotope stages 1-6. The characterization of organic matter is based on hydrogen index (HI) values, n-alkanes and maceral composition, indicating the predominance of terrigenous organic matter through space and time. The variations in the amount and composition of organic carbon are mainly influenced by changes in fluvial sediment supply, Atlantic water inflow, and continental ice sheets. During oxygen isotope stage (OIS) 6, high organic carbon contents in sediments from the Laptev Sea and western East Siberian Sea continental margin were probably caused by the increased glacial erosion and further transport in the eastward-flowing boundary current along the continental margin. During OIS 5 and early OIS 3, some increased amounts of marine organic matter were preserved in sediments east of the Lomonosov Ridge, suggesting an influence of nutrient-rich Pacific waters. During OIS 2, terrigenous organic carbon supply was increased along the Barents and western Kara Sea continental margin caused by extended continental ice sheets in the Barents Sea (Svalbard to Franz Josef Land) area and increased glacial erosion. Along the Laptev Sea continental margin, on the other hand, the supply of terrigenous (organic) matter was significantly reduced due to the lack of major ice sheets and reduced river discharge. Towards the Holocene, the amount of total organic carbon (TOC) increased along the Kara and Laptev Sea continental margin, reaching average values of up to 0.5 g C/cm**2/ky. Between about 8 and 10 ka (9 and 11 Cal ka), i.e., during times when the inner shallow Kara and Laptev seas became largely flooded for the first time after the Last Glacial Maximum, maximum supply of terrigenous organic carbon occurred, which is related to an increase in coastal erosion and Siberian river discharge. During the last 8000 years, the increased amount of marine organic carbon preserved in the sediments from the Kara and Laptev Sea continental margin is interpreted as a result of the intensification of Atlantic water inflow along the Eurasian continental margin.

Accumulation rates and composition of organic matter in sediments off Peru

Deep-sea sediment samples from three Ocean Drilling Program (ODP) Leg 112 sites on the Peru continental margin were investigated, using a number of organic geochemical and organic petrographic techniques, for amounts and compositions of the organic matter preserved. Preliminary results include mass accumulation rates of organic carbon at Site 679 and characteristics of the organic facies for sediments from Sites 679, 681, and 684. Organic-carbon contents are high, with few exceptions. Particularly high values were determined in the Pliocene interval at Site 684 (4%-7.5%) and in the early Pliocene to Quaternary section of Hole 679D (2%-9%). Older sediments at this site have distinctively lower organic-carbon contents (0.2%-2.5%). Mass accumulation rates of organic matter at Site 679 are 0.02 to 0.07 g carbon/cm**2/k.y. for late Miocene to early Pliocene sediments and higher by a factor of 5 to 10 in the Quaternary sediments. The organic matter in all samples has a predominantly marine planktonic and bacterial origin, with minor terrigenous contribution. Organic particle sizes are strikingly small, so that only a minor portion is covered by visual maceral analysis. Molecular organic-geochemical data were obtained for nonaromatic hydrocarbons, aromatic hydrocarbons (including sulfur compounds), alcohols, ketones, esters, and carboxylic acids. Among the total extractable lipids, long-chain unsaturated ketones from Prymnesiophyte algae strongly predominate among the gas chromatography (GC) amenable components. Steroids are major constituents of the ketone and free- and bound-alcohol fractions. Perylene is the most abundant aromatic hydrocarbon, whereas in the nonaromatic hydrocarbon fractions, long-chain n-alkanes from higher land plants predominate, although the total terrigenous organic matter proportion in the sediments is small.

Composition of bitumen in the organic matter of Black Sea sediments from DSDP Hole 42-379B

Bituminologic analysis of sediment cores from the Black Sea (water depth up to 2000 m, drilling depth up to 625 m) has revealed all components typical for fossilized rocks, viz. hydrocarbons, resins, asphaltenes, and insoluble matter. Proportions of these components, their composition and properties do not display any dependence on depth in hole and seem to be governed by composition of organic matter and conditions and degree of its transformation at early stages of lithogenesis.

TOC, CaCO3, n-alkane and alkenone concentrations of ODP Sites 202-1237 and 202-1239

We generated preliminary downcore records of total organic carbon content, calcium carbonate, long-chain n-alkane concentration, total alkenone concentration, and alkenone-based sea-surface temperature for samples from the easternmost flank of Nazca Ridge (Site 1237) and the eastern crest of Carnegie Ridge (Site 1239). Total organic carbon and long-chain n-alkane concentrations will be used to evaluate terrestrial sediment sources. Downcore records of alkenone sea-surface temperature will benefit studies of paleoceanography of the southeastern Pacific. Since these sites are located under the influence of major tectonic events, such as the uplift of the Andes Mountains and the closure of the Isthmus of Panama, the records will help us to examine the effects of the tectonic events on the oceanic environment.

Biomarker proxies on ODP Holes 151-912A and 151-912B

A novel and promising biomarker proxy for reconstruction of Arctic sea ice conditions was developed and is based on the determination of a highly branched isoprenoid with 25 carbons (IP25). IP25 records have been restricted to the last 150 kyr BP. We present a biomarker record from Ocean Drilling Program (ODP) Site 912, going back to the Pliocene-Pleistocene boundary and indicating that sea ice of variable extent occurred in the Fram Strait/southern Yermak Plateau area at least since about 2.2 Ma. Furthermore, our data support the idea that a combination of IP25 and open water, phytoplankton biomarker data ("PIP25 index") may give a more reliable and quantitative estimate of past sea ice cover (at least for the study area). The study reveals that the novel IP25/PIP25 biomarker approach has potential for semi-quantitative paleo-sea ice studies covering the entire Quaternary and could motivate further detailed high resolution research on ODP/IODP material using this proxy.