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.

Sediment investigations in the Kara Sea

AMS-14C dated sediment cores from the Ob and Yenisei estuaries and the adjacent inner Kara Sea were investigated to determine the siliclastic and organic carbon fluxes and their relationship to paleoenvironmental changes. The variability of sediment fluxes during Holocene times is related to the post-glacial sea-level rise and changes in river discharge and coastal erosion input. Whereas during the late/middle Holocene most of the terrigenous sediments were deposited in the estuaries and the areas directly off the estuaries, huge amounts of sediments accumulated on the Kara Sea shelf farther north during the early Holocene before about 9 Cal. kyrs. BP. The maximum accumulation at that time is related to the lowered sea level, increased coastal erosion, and increased river discharge due to the final stage of mountain deglaciation of the Putoran Massif. Increased supply of Yenisei-derived material indicated by peak magnetic susceptibility values probably occurred in climate-related pulses culminating near 11, 10, and 9 Cal. kyrs. BP. As sea level rose, the main Holocene depocenter migrated southward. Based on hydrogen index values and n-alkanes, the organic matter is predominantly of terrigenous origin. Maximum accumulation rates of 1.5 to more than 6 g/cm**2/y occurred in the early Holocene sediments, suggesting more humid climatic conditions with an increased vegetation cover in the source area at that time. In general, high organic carbon accumulation rates characterize the estuaries and the inner Kara Sea as important sink for terrigenous organic carbon. A high-resolution record of Holocene variability of magnetic susceptibility (MS) in an AMS14C-dated sediment core from the northern Yenisei estuary may indicate natural variability of Arctic climate change and river discharge on a centennial to millenial time scale. Short-term maxima in MS probably related to warmer climate, enhanced precipitation, intensified weathering/erosion and increased river discharge, display a frequency of about 300 to 700 years.

Organic geochemical studies of DSDP Leg 64 Holes

Twenty-six core samples from Leg 64, Holes 474, 474A, 477, 478, 479, and 481A in the Gulf of California, were provided by the Joint Oceanographic Institutions for Deep Earth Sampling (JOIDES) Advisory Panel on Organic Geochemistry for analysis. The high heat flow characteristic of the basin provides an opportunity to study the effect of temperature on the diagenesis of organic matter. The contents and carbon isotope compositions of the organic matter and bitumen fractions of different polarity, isoprenoid and normal alkane distributions, and the nature of tetrapyrrole pigments were studied. Relative contents of hydrocarbons and bitumens depend on the thermal history of the deposits. Among other criteria, the nature and content of tetrapyrrole pigments appear to be most sensitive to thermal stress. Whereas only chlorins are present in the immature samples, porphyrins, including VO-porphyrins, appear in the thermally altered deposits, despite the shallow burial depth. Alkane distributions in thermally changed samples are characterized by low values of phytane to 2-C18 ratios and an odd/even carbon preference index close to unity. The thermally altered samples show unusual carbon isotope distributions of the bitumen fractions. The data also provide some evidence concerning the source of the organic matter and the degree of diagenesis.

CPI, d13C, Corg and diploptene from ODP Hole 169-1034B varved sediments

Saanich Inlet has been a highly productive fjord since the last glaciation. During ODP Leg 169S, nearly 70 m of Holocene sediments were recovered from Hole 1034 at the center of the inlet. The younger sediments are laminated, anaerobic, and rich in organic material (1-2.5 wt.% Corg), whereas the older sediments below 70 mbsf are non-laminated, aerobic, with glacio-marine characteristics and have a significantly lower organic matter content. This difference is also reflected in the changes of interstitial fluids, and in biomarker compositions and their carbon isotope signals. The bacterially-derived hopanoid 17alpha(H),21beta(H)-hop-22(29)-ene (diploptene) occurs in Saanich Inlet sediments throughout the Holocene but is not present in Pleistocene glacio-marine sediments. Its concentration increases after ~6000 years BP up to present time to about 70 µg/g Corg, whereas terrigenous biomarkers such as the n-alkane C31 are low throughout the Holocene (<51 µg/g Corg) and even slightly decrease to 36 µg/g Corg at the most recent time. The increasing concentrations of diploptene in sediments younger than ~6000 years BP separate a recent period of higher primary productivity, stronger anoxic bottom waters, and higher bacterial activity from an older period with lesser activity, heretofore undifferentiated. Carbon isotopic compositions of diploptene in the Holocene are between ~31.5 and ~39.6 per mil PDB after ~6000 years BP. These differences in the carbon isotopic record of diploptene probably reflect changes in microbial community structure of bacteria living at the oxic-anoxic interface of the overlying water column. The heavier isotope values are consistent with the activity of nitrifying bacteria and the lighter isotope values with that of aerobic methanotrophic bacteria. Therefore, intermediate delta13C values probably represent mixtures between the populations. In contrast, carbon isotopic compositions of n-C31 are roughly constant at ~31.4 ± 1.1 per mil PDB throughout the Holocene, indicating a uniform input from cuticular waxes of higher plants. Prior to ~6000 years BP, diploptene enriched in 13C of up to -26.3 per mil PDB is indicative of cyanobacteria living in the photic zone and suggests a period of lower primary productivity, more oxygenated bottom waters, and hence lower bacterial activity during the earliest Holocene.

Carbon, hydrocarbon and alkenone composition and indices of ODP Hole 167-1016C sediments

Total organic carbon (TOC) and calcium carbonate (CaCO3) concentrations were determined for 304 samples, and biomarkers were analyzed for 101 samples from Core 167-1016C-1H. TOC varies between 1% and 2%, and CaCO3 is typically 1%-4%, with peaks reaching 14%. Paleotemperature estimated from Uk'37 varies from 8.5° to 17.5°C. The Uk'37 variation implies that Core 167-1016C-1H covers oxygen isotope Stages 1-6. Peaks of diatom-derived C25:1 HBI alkene concentrations occur during warming intervals, suggesting intensified upwelling during deglaciation. The concentrations of haptophyte-derived alkenones and diatom-derived C25:1 HBI alkene vary out of phase, which presumably resulted from the changes in the mode of nutrient supply to surface mixed layer. Maximal CaCO3 contents (>10%) were observed in both warming and cooling intervals. The peak in cooling interval relates to an alkenone maximum, whereas the peaks in warming intervals do not. This implies that carbonate production is not the only factor controlling carbonate compensation depth at this site, and it suggests considering the changes in North Pacific deep-water chemistry. Petroleum-type compounds are present in Site 1016 sediments. Their concentrations are maximized in the warming intervals that correspond to the timing of destruction of a huge tar mound off Point Conception. The tarry material was presumably transported by the Arguello Fan system to Site 1016.

Hydrocarbons in particulate matter and bottom sediments from the north Caspian Sea shelf

Data are presented on content and composition of hydrocarbons (HC) (aliphatic AHC and polyaromatic PAH) in filtered particulate matter and in the surface layer of bottom sediments from the northern shelf of the Caspian Sea and related to data on their contents in the Volga River estuary. Because of transformation and precipitation of anthropogenic and natural compounds, HC composition in particulate matter and bottom sediments undergoes transformations caused by mixing of fresh and saline waters (in bottom sediments, within concentration ranges 70.4-4557.9 µg/g for AHC and 3.8-4800 ng/g for PAH). It was found that the greatest concentrating of HC proceeds in the region of the avalanche sedimentation, and their contents are independent of grain-size types of bottom sediments. Anthropogenic HC (oil and pyrogenous) do not get over the marginal filter of the Volga River and do not pass to the open part of the sea.

Concentration of organic compounds in aerosols and surface waters of the East Atlantic and Antarctic

The data on content and composition of lipids and aliphatic hydrocarbons (HC) in aerosols and surface waters obtained during the spring-summer periods of 2001 and 2003 along the vessel route from the North Sea to the Antarctic and backwards are presented. It was shown that the distribution of organic compounds is caused by influence of zonal supply of eolian matter from land, anthropogenic, and marine autochtonous sources. Concentrations of organic compounds in the aerosols varied from 0.22 to 13.04 ng/m**3 for lipids and from 0.04 to 7.03 ng/m**3 for aliphatic HC; in surface waters, it from 9 to 84 and from 1 to 53 µg/l, respectively. There is correlation between fluxes of lithogenic fraction of the aerosols, HC, and lipids. Growth of productivity in the aquatic area increases levels of the HC in the surface waters but to a lower degree than HC supply with oil contamination.

Organic geochemistry of water and bottom sediments during a seasonal flood in 2006 in the North Dvina River estuary

Heavy contaminant load released into the Northern Dvina River during flooding increased the concentrations of aliphatic (AHC) and polcyclic aromatic (PAH) hydrocarbons in water and bottom sediments. The composition of hydrocarbons was different from that of the summer low flow season. The concentrations of dissolved and particulate AHC ranged from 12 to 106 and from 192 to 599 µg/l, respectively, and bottom sediments contained from 26.2 to 329 µg/g AHC and 4 to 1785 ng/g PAH. As the transformation of AHC occurred at low spring temperatures, the alkane composition was shown to be dominated by terrigenous compounds, whereas more stable PAH showed elevated contents of petrogenic and pyrogenic compounds. It was also shown that the Northern Dvina-Dvina Bay geochemical barrier prevents contaminant input into the White Sea, i.e., acts as a marginal filter.

Composition of organic matter in suspended matter and bottom sediments of the southeastern Baltic Sea

Data on contents and compositions of hydrocarbons (HCs)-aliphatic (AHCs) and polycyclic aromatic (PAHs) are provided in comparison with contents of total organic carbon (Corg), lipids in suspended matter, and Corg in bottom sediments. Particular attention is paid to distribution of HCs in the area of the Kravtsov oil field. It is established that concentrations of AHCs in water are governed by concentrations of suspended matter and elevated AHC concentrations are confined to coastal areas. In the area of D-6 platform sandy bottom sediments are notable for great variability of HC concentrations, both laterally and from year to year. In summer of 2010 average content of AHCs was 40 ppm (19% of Corg) and that of PAHs was 0.023 ppm. Natural seepage from sediment mass is considered to be a source of HCs along with oil contamination.

Composition of rocks, minerals, water, and gases from uplift areas of the Central Atlantic

Original geological, geophysical, lithological, mineralogical data on uplifts of the Central Atlantic are given in the book based on materials of Cruise 1 of the R/V Akademik Nikolaj Strakhov. Geological and geophysical studies include description of the obtained material and analysis of structural and morphological elements of the ocean floor. Results of lithological, petrochemical and geochemical studies were extremely innovative and develop a conceptual model. The latter include studies of petrochemical evolution of tholeiitic alkaline plate volcanism, large-scale hydrothermal transformation of basement rocks - palygorskitization, phosphatization and ferromanganese mineralization. Showing imposition Superposition of hydrogenic alteration on hydrothermally altered rocks and its role in Cenozoic history of sedimentation is shown.

Hydrogen isotopic composition of sediment cores from a transect off western Africa

The hydrogen isotopic composition of plant leaf-wax n-alkanes (dDwax) is a novel proxy for estimating dD of past precipitation (dDp). However, vegetation life-form and relative humidity exert secondary effects on dDwax, preventing quantitative estimates of past dDp. Here, we present an approach for removing the effect of vegetation-type and relative humidity from dDwax and thus for directly estimating past dDp. We test this approach on modern day (late Holocene; 0-3 ka) sediments from a transect of 9 marine cores spanning 21°N-23°S off the western coast of Africa. We estimate vegetation type (C3 tree versus C4 grass) using d13C of leaf-wax n-alkanes and correct dDwax for vegetation-type with previously-derived apparent fractionation factors for each vegetation type. Late Holocene vegetation-corrected dDwax (dDvc) displays a good fit with modern-day dDp, suggesting that the effects of vegetation type and relative humidity have both been removed and thus that dDvc is a good estimate of dDp. We find that the magnitude of the effect of C3 tree - C4 grass changes on dDwax is small compared to dDp changes. We go on to estimate dDvc for the mid-Holocene (6-8 ka), the Last Glacial Maximum (LGM; 19-23 ka) and Heinrich Stadial 1 (HS1; 16-18.5 ka). In terms of past hydrological changes, our leaf-wax based estimates of dDp mostly reflect changes in wet season intensity, which is complementary to estimates of wet season length based on leaf-wax d13C.

Lipid biomarkers in urface sediments of the Southeast Atlantic

Surface sediments from the eastern South Atlantic were investigated for their lipid biomarker contents and bulk organic geochemical characteristics to identify sources, transport pathways and preservation processes of organic components. The sediments cover a wide range of depositional settings with large differences in mass accumulation rates. The highest marine organic carbon (OC) contributions are detected along the coast, especially underlying the Benguela upwelling system. Terrigenous OC contributions are highest in the Congo deep-sea fan. Lipid biomarker fluxes are significantly correlated to the extent of oxygen exposure in the sediment. Normalization to total organic carbon (TOC) contents enabled the characterization of regional lipid biomarker production and transport mechanisms. Principal component analyses revealed five distinct groups of characteristic molecular and bulk organic geochemical parameters. Combined with information on lipid sources, the main controlling mechanisms of the spatial lipid distributions in the surface sediments are defined, indicating marine productivity related to river-induced mixing and oceanic upwelling, wind-driven deep upwelling, river-supply of terrigenous organic material, shallow coastal upwelling and eolian supply of plant-waxes.