Organic geochemistry of Upper Albian sediments from the Kirchrode I borehole

In the framework of a multidisciplinary research program, an organic geochemical study was carried out on a drill core which comprises a 245 m thick sequence of light-colored, Upper Albian marlstones that were deposited in the central part of the Lower Saxony basin (northern Germany). For part of the Upper Albian sequence, high-resolution measurements of carbonate contents reveal cycles which can be related to earth orbital forcing. Based on these data, sediment accumulation rates were calculated to be in the order of 15 g/m**2/yr. These high accumulation rates contrast with very low organic carbon contents and an extremely poor preservation of the autochthonous organic matter. Most of the sedimentary organic matter is of terrigenous origin and mainly derived from the erosion of older sedimentary rocks. Organic petrography reveals only a very small fraction of marine organic particles. Carbon/sulphur ratios, pristane/phytane ratios as well as the predominance of resedimented organic particles over autochthonous organic particles suggest that aerobic degradation processes rather than anaerobic processes (sulphate reduction) were responsible for the degradation of the organic matter. Furthermore, the scarcity of terrigenous organic particles (vitrinite) indicates that there was little vegetation on nearby land areas. To explain these analytical results, a depositional model was developed which could explain the scarcity of organic matter in the Upper Albian sediments. This model is based on downwelling of oxygen-rich, saline waters of Tethyan origin, which reduces the nutrient content of surface waters and thus primary bioproductivity while degradation of primary organic matter in the water column is enhanced at the same time. These conditions contrast to those which existed in Barremian and early Aptian times in this basin, when limited water exchange with adjacent oceans caused oxygen deficiency and the deposition of numerous organic carbon-rich black shales. The thick, organic matter-poor Upper Albian sequence of northern Germany also contrasts with comparatively thin, time-equivalent, deep-sea black shales from Italy. This discrepancy indicates that local and regional oceanographic factors (at least in this case) have a greater influence on organic matter deposition than global events.

Organic geochemistry of DSDP Site 467

Results of the analyses of twenty-three samples from the Middle Miocene to Lower Pliocene strata from DSDP Site 467, offshore California, are presented. The analyses were performed with the aim of determining the origin of the organic matter, the stratigraphic section's hydrocarbon generation potential and extent of organic diagenesis. Organic carbon contents are an order of magnitude greater than those typically found in deep sea sediments, suggesting an anoxic depositional environment and elevated levels of primary productivity. Hydrocarbon generation potentials are above average for most samples. The results of elemental analyses indicate that the kerogens are primarily composed of type II organic matter and are thermally immature. Analysis of the bitumen fractions confirms that the samples are immature. In cores from 541 to 614 meters, the gas chromatograms of the C15+ non-aromatic hydrocarbon fractions are dominated by a single peak which was identified as 17*(H), 18*(H), 21beta(H)-28, 30-bisnorhopane. This interval is the same area in which the highest degrees of anoxia are observed as reflected by the lowest pristane/phytane ratios. This correlation may have some implications with regard to the origin of the bisnorhopane and its possible use as an indicator of anoxic depositional conditions within thermally immature sediments.

Hydrocarbons in hydrothermal sulfides from the Rainbow Hydrothermal Field

The Rainbow Hydrothermal Field (36°N, Mid-Atlantic Ridge) is one of three presently known fields related to serpentinization of ultramafic rocks accompanied by formation of hydrogen- and methane rich solutions. Gas chromatographic and molecular gas chromatographic - mass spectrometric investigations of sulfide ores and sediments from this field confirmed predominantly biological nature of bitumoids related to high-temperature transformation of biomass of the hydrothermal biological community. At the same time ores of the Rainbow field contain significant amounts of compounds that are not directly related to biogenic synthesis. This fact suggests possibility of abiogenic synthesis of methane and even complex hydrocarbons during serpentinization of ultramafic rocks.

Data on multidisciplinary research in the Tajura Rift (Gulf of Aden) during Cruise 7 of R/V Akademik Mstislav Keldysh in winter 1983-1984

In the collective monograph results of geological and geophysical studies in the Tadjura Rift carried out by conventional outboard instruments and from deep/sea manned submersibles "Pisces" in winter 1983-1984 are reported. Main features of rift tectonics, geology, petrology, and geochemistry of basalts from the rift are under consideration. An emphasis is made on lithology, stratigraphy, and geochemistry of bottom sediments. Roles of terrigenous, edafogenic, biogenic, and hydrothermal components in formation of bottom sediments from the rift zone are shown.

Pleistocene and upper Pliocene sapropels in the Tyrrhenian Sea, Mediterranean Sea

A most significant finding of the ODP Leg 107 drilling campaign was the recovery of at least 56 distinct sapropel intervals in upper Pliocene to Pleistocene sediments of six sites drilled in the Tyrrhenian Sea. Except for 3 repots of disturbed organic-rich sediments - recovered in Core 201 of the Swedish Deep-Sea Expedition, in Core 2R-1,107 cm of Site 373 (Leg 13 DSDP) and at Site 373, Core 1-2,O-5 cm of DSDP Leg 42A - sapropels had previously only been described from the eastern Mediterranean and the Black Sea. Scientific deep-sea drilling in the Tyrrhenian Sea during DSDP Legs 13 and 42A apparently missed most of these deposits due to spot coring and rotary drilling techniques; high sedimentation rates may have precluded recovery by conventional gravity coring devices. The recovery of multiple layers of sapropels and sapropelic sediments in the Tyrrhenian Sea demonstrates that oceanographic conditions conducive to sapropel formation were not confined to the Black Sea and eastern Mediterranean, but occurred sporadically and possibly simultaneously in the entire Mediterranean during the Pliocene and Pleistocene. In the light of this finding, previous models of sapropel genesis may need reconsideration. In this paper, we present some initial data on the Tyrrhenian sapropels and suggest some implications of their massive occurrence in the western Mediterranean realm. We end by outlining possible causes for deposition of sapropels in an attempt to revive the interest in sapropels and their paleoceanographic significance.

Organic chemistry of sediments of the Peru margin

Organic-carbon-rich anoxic sediments from the continental shelf (Site 680) and the lower continental slope (Site 688) off Peru were studied to determine factors controlling the accumulation of reduced sulfur. High concentrations of organic matter in diatomaceous muds, its thermal immaturity, and the presence of abundant hydrogen-containing organic compounds lead to the conclusion that organic matter is not limiting for reduced sulfur formation. Rather, high degrees of iron pyritization at Site 680 limit pyrite accumulation in sediments from this shelf site. The low degree of iron pyritization and nearly complete reduction of dissolved sulfate at Site 688 suggest that a lack of interstitial sulfate is limiting pyrite formation there. Although factors that limit the formation of sedimentary iron sulfide are different at each site, the resulting average reduced-sulfur concentrations are remarkably similar (0.85 wt.% at Site 680 and 0.86 wt.% at Site 688). Carbon to sulfur (C/S) ratios are higher in samples containing in excess of 3 wt.% organic carbon than the average of 2.8 in normal marine sediments and have been primarily influenced by variations in organic matter concentrations.

Sea ice diatoms from Late Quaternary sediments in the Scotia Sea

Sea-ice growth and decay in Antarctica is one of the biggest seasonal changes on Earth, expanding ice cover from 4x10**6 km**2 to a maximum of 19x10**6 km**2 during the austral winter. Analyses of six marine sediment cores from the Scotia Sea, SW Atlantic, yield records of sea-ice migration across the basin since the Lateglacial. The cores span nearly ten degrees of latitude from the modern seasonal sea-ice zone to the modern Polar Front. Surface sediments in the cores comprise predominantly diatomaceous oozes and muddy diatom oozes that reflect Holocene conditions. The cores exhibit similar down-core stratigraphies with decreasing diatom concentrations and increasing magnetic susceptibility from modern through to the Last Glacial Maximum (LGM). Sediments in all cores contain sea-ice diatoms that preserve a signal of changing sea-ice cover and permit reconstruction of past sea-ice dynamics. The sea-ice records presented here are the first to document the position of both the summer and winter sea-ice cover at the Last Glacial Maximum (LGM) in the Scotia Sea. Comparison of the LGM and Holocene sea-ice conditions shows that the average winter sea-ice extent was at least 5° further north at the LGM. Average summer sea-ice extent was south of the most southerly core site at the LGM, and suggests that sea-ice expanded from approximately 61°S to 52°S each season. Our data also suggest that the average summer sea-ice position at the LGM was not the maximum extent of summer sea-ice during the last glacial. Instead, the sediments contain evidence of a pre-LGM maximum extent of summer sea-ice between ab. 30 ka and 22 ka that extended to ab. 59°S, close to the modern average winter sea-ice limit. Based on our reconstruction we propose that the timing of the maximum extent of summer sea-ice and subsequent retreat by 22 ka, could be insolation controlled and that the strong links between sea-ice and bottom water formation provide a potential mechanism by which Southern Hemisphere regional sea-ice dynamics at the LGM could have a global impact and promote deglaciation.

Organic carbon chemistry of late Tertiary to Quaternary sediments ODP Leg 107

We analyzed samples from ODP Holes 652A and 654A (Leg 107, Tyrrhenian Sea) for the amount, type, and thermal maturity of organic matter. The sediments encompass clastic and biogenic lithologies, which were deposited on the passive margin east of Sardinia since the late Miocene to the Pleistocene. Marine, hypersaline/evaporitic, lacustrine/riverine, and finally hemipelagic marine conditions with occasional anoxic(?) interludes gave rise to very diverse sedimentary facies. The majority of samples is lean in organic matter (<0.2% TOC). Notable exceptions are Tortonian sediments (TOC average 0.3%), Messinian oil shales from Core 107-652A-64R (up to 11% TOC), Messinian lacustrine/fluvial sediments from Hole 652A (TOC average 0.42%,), and Pleistocene sapropel samples (>2% TOC). The Messinian oil shale in Hole 652A appears to be the only mature hydrocarbon source rock. In general, Pliocene sediments are the leanest and least mature samples. Pleistocene and Pliocene samples derive organic matter from a marine source. In spite of obvious facies differences in the Messinian between the two sites, pyrolysis results are not conclusive in separating hypersaline facies of Site 654 from the fresh water facies of Site 652, because both appear to have received terrestrial organic tissue as the main component of TOC. It is apparent from the distribution of maximum pyrolysis temperatures that heat flow must have been considerably higher at Site 652 on the lower margin in the Messinian. Molecular maturity indices in lipid extracts substantiate the finding that the organic matter in Tortonian and Messinian samples from Hole 654A is immature, while thermal maturation is more advanced in coeval samples from Hole 652A. Analyses of lipid biomarkers showed that original odd-even predominance was preserved in alkanes and alkylcyclohexanes from Messinian samples in Hole 654A, while thermal maturation had removed any odd-even predominance in Hole 652A. Isomerization data of hopanes and steranes support these differences in thermal history for the two sites. Hopanoid distribution further suggests that petroleum impregnation from a deeper, more mature source resulted in the co-occurrence of immature and mature groups of pentacyclic biomarkers. Even though the presence of 4-methylsteranes may imply that dinoflagellates were a major source for organic matter in the oil shale interval of Hole 652, we did not find intact dinoflagellates or related nonskeletal algae during microscopic investigation of the organic matter in the fine laminations. Morphologically, the laminations resemble bacterial mats.

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.

Siliceous microplankton in surface sediments and the water column of the Red Sea

We studied the siliceous microplankton assemblages (mainly diatoms) from plankton tows (mesh size 20 µm) and surface sediment samples collected along a N-S transect in the northern Red Sea (28-21°N). In addition, we analyzed differences/similarities between plankton and sediment assemblages within a brine-filled basin (the southern basin) of the Shaban Deep and compared these assemblages with those from outside the brine. Plankton samples revealed the overwhelming dominance of diatoms over other siliceous groups. Diatoms accounted for ca. 97% of all biosiliceous particles at 120-20 m (vs. 2.9% silicoflagellates and 0.4% radiolarians), and ca. 94% at 200-120 m (vs. 4.5% silicoflagellates and 1.6% radiolarians). In general, a marine, warm-water (tropical/subtropical) diatom assemblage characterizes the plankton samples. Representatives of the Nitzschia bicapitata group are by far the most abundant contributors at both depth intervals (average=43%), ranging from ca. 30% in the North to ca. 60% in the South. Biogenic opal content in non-brine surface sediments is very low, (below 0.2 wt.% SiO2); and concentration of siliceous microorganisms is also low and of the order of 5*10**3-10**4 microorganisms/g dry sediment. Diatoms are the main contributors to the opal signal in the 20-40 µm fraction, while they share dominance with radiolarians in the >40 µm fraction. Total diatom concentrations average 1.2*10**4 valves/g in the 20-40 µm fraction and 4*10**3 valves/g in the >40 µm fraction. Robust taxa of warm water affinity (Alveus marinus, Azpeitia neocrenulata, Azpeitia nodulifera and Roperia tesselata) characterize the surface sediments. In contrast, biogenic opal content in brine surface sediment samples is much higher than in the non-brine samples, ranging from 2.8 to 3.8 wt.% SiO2, and concentration of siliceous microorganisms is 3-4 orders of magnitude higher. In addition here, diatoms dominate the opal signal. The taxa found in these samples are a mixture of non-brine and plankton samples, and fragile forms (e.g., N. bicapitata group, Neodelphineis indica) are well preserved in these sediments. Thus, brine sediments in this region seem to offer a great potential for palaeoenvironmental studies.

Mineralogical, sedimentological and paleontological analyses of ODP Hole 127-797B upper Quarternary sediments

Nearly continuous cores of Quaternary fine-grained sediments with distinct dark-light colored cycles were recovered from Sites 794, 795, and 797 in the basinal parts of the Japan Sea during Leg 127. A comparison of gray value (darkness) profiles supplemented by visual inspection of core photographs between sites indicated that most of the dark and light layers were correlatable between sites, and that two of the dark layers lie close to adjacent marker ash layers. These observations indicate that deposition of dark and light layers resulted from basin-wide synchronous events. In order to understand the origin of these dark-light cycles, petrographical, mineralogical, compositional, and paleontological studies were carried out on closely spaced samples from the upper Quaternary sediments recovered from Site 797. Age model was constructed based on comparison between variation in diatom abundance and the standard oxygen isotope curve of Imbrie et al. (1984), the latter was interpolated between the five age controlled levels established at Site 797. The two curves show similar patterns which enabled us to "tune" the sediment ages to the oxygen isotope stages. We have to use variation in diatom abundance as a substitute for oxygen isotope curve since oxygen isotopic data are not available at the studied sites. Bottom water oxygenation conditions were estimated based on two criteria: (1) the degree of lamina preservation and (2) the ratio of Corg to Stot. The surface water productivity was deduced from the Corg and biogenic silica content. Results suggest that the bottom water oxygenation level and the surface water productivity varied significantly in response to the glacial-interglacial cycles. Glacio-eustatic sea-level changes and subsequent changes in water circulation in the Japan Sea appear to have been responsible for these variations and consequent changes in sediment composition throughout the Quaternary.

n-Alkane, fatty acid and hopanoic acid concentrations of ODP Site 190-1178 samples

Ocean Drilling Program (ODP) Leg 190 was programmed to investigate deformational, diagenetic, and hydrologic processes and their interactions in the Nankai Trough accretionary prism. Site 1178 is the northernmost site in the Muroto Transect. Slope sediments and the underlying landward-dipping reflector zone were successfully cored. Temperature measurements and Cl concentrations in pore water indirectly indicate the presence of gas hydrate between 120 and 400 meters below seafloor (mbsf) at Site 1178, with the highest concentrations between 150 and 200 mbsf (Shipboard Scientific Party, 2001, doi:10.2973/odp.proc.ir.190.109.2001). Sedimentary structures show a broad range of deformation structures rich in fractures, suggesting active fluid circulation in the Nankai Trough prism. One of the objectives of Leg 190 was to clarify the interplay of various fundamental processes taking place in the Nankai Trough accretionary prism. Bacteria or prokaryotes in deep subsurface sediment play an important role for material transformation and circulation in an accretionary prism. Significant amounts of bacteria are detected in many of the samples examined (Shipboard Scientific Party, 2001, doi:10.2973/odp.proc.ir.190.109.2001). The type of organic matter in sediments is an important factor related to bacterial activity. To assist investigations on material circulation in deep subsurface sediments, the samples from Site 1178 were analyzed for geolipids (extractable organic matter). The basic data set is preliminarily compiled in the present report to show the types of organic matter and their concentrations in sediments from Site 1178.

Low-molecular-weight hydrocarbons in sediments of Broken Ridge and Ninetyeast Ridge

Core samples taken during Leg 121 drilling aboard the JOIDES Resolution in the central Indian Ocean were analyzed for their low-molecular-weight hydrocarbon contents. Forty-three samples from the Broken Ridge and 39 samples from the Ninetyeast Ridge drill sites, deep-frozen on board immediately after recovery, were studied by a dynamic headspace technique (hydrogen-stripping/thermovaporization). Light hydrocarbons (saturated and olefinic) with two to four carbon atoms, and toluene as a selected aromatic compound, were identified. Total C2-C4 saturated hydrocarbon yields vary considerably from virtually zero in a Paleogene calcareous ooze from Hole 757B to nearly 600 nanogram/gram of dry-weight sediment (parts per billion) in a Cretaceous claystone from Hole 758A. An increase of light-hydrocarbon yields with depth, and hence with sediment temperature, was observed from Hole 758A samples down to a depth of about 500 meters below seafloor. Despite extreme data scatter due to lithological changes over this depth interval, this increased yield indicates the onset of temperature-controlled hydrocarbon formation reactions. Toluene contents are also extremely variable (generally between 10 and 100 ppb) and reach more than 300 ppb in two samples of tuffaceous lithology (Sections 121-755A-17R-4 and 121-758A-48R-4). As for the saturated hydrocarbons, there was also an increase of toluene yields with increasing depth in Hole 758A.

Alkenones and TEX86 temperature proxies for core-top sediments from the southern Adriatic Sea

The Mediterranean Sea is at the transition between temperate and tropical air masses and as such of importance for studying climate change. The Gulf of Taranto and adjacent SW Adriatic Sea are at the heart of this region. Their sediments are excellently suited for generating high quality environmental records for the last millennia with a sub-decadal resolution. The quality of these records is dependent on a careful calibration of the transfer functions used to translate the sedimentary lipid signals to the local environment. Here, we examine and calibrate the UK'37 and TEX86 lipid-based temperature proxies in 48 surface sediments and relate these to ambient sea surface temperatures and other environmental data. The UK'37-based temperatures in surface sediments reflect winter/spring sea surface temperatures in agreement with other studies demonstrating maximum haptophyte production during the colder season. The TEX86-based temperatures for the nearshore sites also reflect winter sea surface temperatures. However, at the most offshore sites, they correspond to summer sea surface temperatures. Additional lipid and environmental data including the distribution of the BIT index and remote-sensed chlorophyll-a suggest a shoreward increase of the impact of seasonal and spatial variability in nutrients and control of planktonic archaeal abundance by primary productivity, particle loading in surface waters and/or overprint by a cold-biased terrestrial TEX86 signal. As such the offshore TEX86 values seem to reflect a true summer signal to the effect that offshore UK'37 and TEX86 reconstruct winter and summer temperature, respectively, and hence provide information on the annual temperature amplitude.