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.

Temporal and spatial LGM variability of biomarker records in the Arctic Ocean

Using the sea ice proxy IP25 and phytoplankton-derived biomarkers (brassicasterol and dinosterol) Arctic sea-ice conditions were reconstructed for Marine Isotope Stage (MIS) 3 to 1 in sediment cores from the north of Barents Sea continental margin across the Central Arctic to the Southern Mendeleev Ridge. Our results suggest more extensive sea-ice cover than present-day during MIS 3, increasing sea-ice growth during MIS 2 and decreased sea-ice cover during the last deglacial. The summer ice edge sustained north of the Barents Sea even during extremely cold (i.e., Last Glacial Maximum (LGM)) as well as warm periods (i.e., Bølling-Allerød). During the LGM, the western Svalbard margin and the northern Barents Sea margin areas were characterized by high concentrations of both IP25 and phytoplankton biomarkers, interpreted as a productive ice-edge situation, caused by the inflow of warm Atlantic Water. In contrast, the LGM high Arctic proper (north of 84°N) was covered by thick permanent sea ice throughout the year with rare break up, indicated by zero or near-zero biomarker concentrations. The spring/summer sea-ice margin significantly extended southwards to the southern Lomonosov Ridge and Mendeleev Ridge during the LGM. Our proxy reconstructions are very consistent with published model results based on the North Atlantic/Arctic Ocean Sea Ice Model (NAOSIM).

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.

Hydrocarbons in bottom sediments during a seasonal flood 2005 in the Dvina River estuary

The results of studying hydrocarbons during the flood in May 2005 are discussed. The concentration of aliphatic and polycyclic aromatic hydrocarbons are shown to match their concentrations in water areas with steady input of pollutants. Weathered oil and pyrogenic compounds dominated in their composition. The geochemical barrier the Northern Dvina River-Dvina Gulf is shown to become a filter during floods and prevents pollutants from penetrating into the White Sea.

Geochemical and optical study of organic matter in some Pleistocene and Pliocene sediments at DSDP Leg 64 Holes

Pleisto-Pliocene hemipelagic and diatomaceous mud was recovered from Deep Sea Drilling Project (DSDP) Sites 474 through 481 in the Gulf of California. The organic matter is mostly marine and mainly derived from diatomaceous protoplasm. We found some continental organic matter in sediments near the bottom basalts or near dolerites (Holes 474A and 478). The organic matter in most of the samples is in an early stage of evolution.

Physical properties of four profiles from the Triassic in Germany

The Norian Steinmergel-Keuper (SMK) represents a low-latitude cyclically-bedded playa system of the Mid-German Basin. We investigated a drilling site (core Morsleben) and sections from marginal positions. Dolomite/red mudstone beds form rhythmic alternations that were associated with varying monsoon activity. Hence, low K/Al ratios of dolomite beds suggest increased chemical weathering of the crystalline hinterland and therefore increased monsoonal rainfall. High K/Al ratios in red mudstone beds reflect increased physical weathering of the hinterlands during dryer periods. Dolomite layers reflect the lake stage (maximum monsoon) while red mudstones indicate the dry phase (minimum monsoon) of the playa cycle. We distinguished five major types of cyclic facies alternations, representing specific facies zones in the playa system. We have implemented spectrophotometry as a tool for high-resolution cyclostratigraphy. The dense sampling increment (up to 1 cm) allows for the recognition of all orbital frequencies. Sediment colour profiles reveal striking hierarchical cycles from semi-precession (SP, 99 kyr) over precession (P, 19.8 kyr) and obliquity (O, 36 kyr) to eccentricity (E1-2 109 kyr; E3, 413 kyr). A significant about 2 Myr-signal is attributed to the longer-term eccentricity E4. One monsoonal (precession) cycle includes two carbonate precipitation events. We propose that stratified mudstone and red mudstone are associated with maximum and minimum monsoon during the transition of the solstices in perihelion and aphelion, respectively. The two carbonate precipitation events were most likely created when equinoxes were in perihelion and aphelion, respectively. A sedimentary semi-precession response cycle is a novel finding for the Norian strata. The obliquity signal is attributed to incoming atmospheric moisture from the northeast of the SMK basin. The E4 cycle controls lake-level changes over long times. Apparently, E4 is responsible whether or not a threshold value is crossed. Bundles of 109 kyr and 413 kyr in red mudstones suggest a dry system with reduced monsoonal activity. In contrast, humid periods reveal thick layers of dolomite beds, indicating that during those intervals the monsoonal activity was strong enough to prevent the playa system from drying out completely.

Facies and diagenesis of organic matter in sediments at DSDP Leg 87

A series of upper Pliocene to Pleistocene sediment samples from DSDP Sites 582 and 583 (Nankai Trough, active margin off Japan) were investigated by organic geochemical methods including organic carbon determination, Rock- Eval pyrolysis, gas chromatography of extractable hydrocarbons, and kerogen microscopy. The organic carbon content is fairly uniform and moderately low (0.35 to 0.77%) at both sites, although accompanied by high sedimentation rates. The low organic matter concentrations are the result of the combined effect of several factors: low bioproductivity, oxic depositional environment, and dilution with lithogenic material. Organic petrography revealed a mixture of three maceral types: (1) fresh, green fluorescent alginites of aquatic origin probably transported by turbidites from the shelf edge, (2) gelified huminites and paniculate liptinites derived from the erosion of unconsolidated peat, and (3) highly reflecting inertinites derived from continental erosion. By a combination of organic petrography and Rock-Eval pyrolysis results, the organic matter is characterized as mainly type III kerogen with a slight tendency to a mixed type II-III. During Rock-Eval pyrolysis, a mineral matrix effect on the generated hydrocarbons was observed. The organic matter in all sediments has a low level of maturity (below 0.45% Rm) and has not yet reached the onset of thermal hydrocarbon generation according to several geochemical maturation parameters. This low maturity is in contrast to anomalously high extract yields at both sites and large hydrocarbon proportions in the extracts at Site 583. This contrast may be due to early generation of polar compounds and perhaps redistribution of hydrocarbons caused by subduction tectonics. Carbon isotope data of the interstitial hydrocarbon gases indicate their origin from bacterial degradation of organic matter, although only very few bacterially degraded maceral components were detected.

Geochemical records of sediment cores from the Sea of Japan

Intervals of organic C- and carbonate-rich laminated sediments occur in the Sea of Japan with roughly the same frequency as temperature changes observed in Greenland ice cores, providing clear evidence of rapid oceanographic change during the past 36 kyr. Planktonic foraminiferal d18O data suggest that only the laminated sediments deposited during the Last Glacial Maximum (LGM), and perhaps one other interval formed during a period of increased water column stratification. Sedimentary Re and Mo data are consistent with bottom waters that were sulfidic during the LGM and suboxic during other laminated intervals. Results of a numerical model of Corg and Re burial are consistent with a mechanism whereby an increased Corg flux to the seafloor drove oxygen concentrations toward depletion during times of deposition of the suboxic laminated intervals. Such a process could have resulted from increased upwelling driven either by increased deep water formation due to colder and/or more saline surface waters or by stronger northeasterly monsoonal winds.

Lithology, stratigraphy, organic carbon content, extract and liquid chromatography yields, and Rock-Eval pyrolysis at DSDP Holes 75-530A and 75-532

Seventeen sediment samples of Albian-Cenomanian to early Pliocene age from DSDP Hole 530A in the Angola Basin and six sediment samples of early Pliocene to late Pleistocene age from the Walvis Ridge were investigated by organic geochemical methods, including organic carbon determination, Rock-Eval pyrolysis, gas chromatography and combined gas chromatography/mass spectrometry of extractable hydrocarbons, and kerogen microscopy. The organic matter in all samples is strongly influenced by a terrigenous component from the nearby continent. The amount of marine organic matter present usually increases with the total organic carbon content, which reaches an extreme value of more than 10% in a Cenomanian black shale from Hole 530A. At Site 530 the extent of preservation of organic matter in the deep sea sediments is related to mass transport down the continental slope, whereas the high organic carbon contents in the sediments from Site 532 reflect both high bioproductivity in the Benguela upwelling regime and considerable supply of terrigenous organic matter. The maturation level of the organic matter is low in all samples.

High-resolution IP25 of three sediment cores in the western North Pacific and Bering Sea

Due to its strong influence on heat and moisture exchange between the ocean and the atmosphere, sea ice is an essential component of the global climate system. In the context of its alarming decrease in terms of concentration, thickness and duration, understanding the processes controlling sea-ice variability and reconstructing paleo-sea-ice extent in polar regions have become of great interest for the scientific community. In this study, for the first time, IP25, a recently developed biomarker sea-ice proxy, was used for a high-resolution reconstruction of the sea-ice extent and its variability in the western North Pacific and western Bering Sea during the past 18,000 years. To identify mechanisms controlling the sea-ice variability, IP25 data were associated with published sea-surface temperature as well as diatom and biogenic opal data. The results indicate that a seasonal sea-ice cover existed during cold periods (Heinrich Stadial 1 and Younger Dryas), whereas during warmer intervals (Bølling-Allerød and Holocene) reduced sea ice or ice-free conditions prevailed in the study area. The variability in sea-ice extent seems to be linked to climate anomalies and sea-level changes controlling the oceanographic circulation between the subarctic Pacific and the Bering Sea, especially the Alaskan Stream injection though the Aleutian passes.

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.

Composition of organic carbon at ODP Site 128-798

Organic geochemical and sedimentological investigations have been performed on sediments from ODP Sites 798 and 799 in order to reconstruct the depositional environment in the Japan Sea through late Cenozoic times. The Miocene to Quaternary sediments from Site 798 (Oki Ridge) and Site 799 (Kita-Yamato Trough) are characterized by high organic carbon contents of up to 6%. The organic matter is mainly a mixture of marine and terrigenous material. The dominant factors controlling marine organic carbon enrichment in the sediments of Hole 798A are probably an increased surface-water productivity and/or an increased preservation rate of organic carbon under anoxic deep-water conditions. In lower Pliocene sediments at Site 798 and Miocene to Quaternary sediments at Site 799, rapid burial of organic matter in turbidites may have been important, too. Remarkable cycles of dark, laminated sediments distinctly enriched in (marine) organic carbon by up to 5% and light, bioturbated to homogeneous sediments with reduced organic carbon contents indicate dramatic short-term paleoenvironmental variation.