Biomarker distributions and calculated sea surface temperatures from the North Pacific Ocean

In order to study the modern sea surface characteristics of the sub-polar North Pacific and the Bering Sea, i.e. sea surface temperature (SST) and sea ice cover, surface sediments recovered during the RV Sonne Expedition 202 in 2009 were analysed. To distinguish between marine and terrestrial organic carbon, hydrogen index values, long chain n-alkanes and specific sterols have been determined. The results show that in the Bering Sea, especially on the sea slope, the organic carbon source is mainly caused by high primary production. In the North Pacific, on the other hand, the organic material originates predominantly from terrestrial higher plants, probably related to dust input from Asia. SST has been reconstructed using the modified alkenone unsaturation index. Calibration from Müller et al. (1998, doi:10.1016/S0016-7037(98)00097-0) offers the most reliable estimate of mean annual temperature in the central North Pacific but does not correlate with mean annual temperature throughout the study area. In the eastern North Pacific and the Bering Sea, the Sikes et al. (1997, doi:10.1016/S0016-7037(97)00017-3) calibration seems to be more accurate and matches summer SST. The distribution of the novel sea ice proxy IP25 (highly branched C25 isoprenoid alkene) in surface sediments is in accord with the modern spring sea ice edge and shows the potential of this proxy to track past variation in sea ice cover in the study area.

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.

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.

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.

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.

Geochemical characterizations of the Cretaceous formations at DSDP Holes 93-603B and 11-105

Geochemical characterizations of the Cretaceous formations at Site 603 are quite comparable with those at Site 105. In the Blake-Bahama and the Hatteras formations, the petroleum potential is medium (<5 kg HC/t of rock) to very low (<0.5 kg HC/t of rock), and the organic matter is mainly of type III origin, that is, terrestrial. At the top of the Hatteras Formation, there is a condensed series, which chiefly contains organic matter of type II origin, with up to 20 wt.% total organic carbon content in Core 603B-34 and 25 wt.% in Core 105-9. This accumulation corresponds to the Cenomanian/Turonian boundary event. An examination of dinoflagellates in the kerogen concentration assigns dates to the samples studied by organic geochemistry. The Cenomanian and Turonian age of the organic-matter-rich black claystones indicates a low rate of sedimentation, about 1 m/Ma. Furthermore, the occurrence of type II organic matter indicates an anoxic environment with insufficient oxygen renewal to oxidize the sinking hemipelagic organic matter. This organic enrichment is not related to local phenomena but to sedimentation over an extended area, because deposits are well known in various areas with different paleodepths in the North Atlantic.

Terrestrial organic matter in marine sediments of the Central Equatorial Atlantic

Terrestrial organic matter (OM) in pelagic sediments is discussed with regard to depositional processes and land-sea interactions in the modern and past glacial/interglacial Equatorial Atlantic. Special emphasis is placed on a critical evaluation of different analytical approaches (C/N, Rock-Eval Pyrolysis, stable carbon isotopes, palynology, organic petrology, and selected biomarkers) which are currently used for the qualitative and quantitative assessment of terrigenous organic carbon. If binary mixing equations are used to calculate terrestrial and marine proportions of organic carbon, we consider the definition of endmember values to be most critical since these values may be biased by a great number of independent controls. A combination of geochemical methods including optical studies (organic petrology and palynology) is therefore suggested to evaluate each individual proxy. Organic geochemical analyses performed on sediments from the modern and Late Quaternary Equatorial Atlantic evidence fluctuations in eolian supply of terrigenous OM related to changes in intensity of the trade winds. Quantification of this organic fraction leads to differing proportions depending on the approach applied, i.e. the organic carbon isotopic composition or maceral analyses. Modern distribution of terrigenous OM reveals a decrease in supply towards the basin contributing less than a fifth of the total OM in pelagic areas. Organic geochemical data indicate that sedimentation in the modern northeastern Brasil Basin is affected by lateral advection of reworked OM probably from southern source areas. Glacial/interglacial deposits from the pelagic Equatorial Atlantic (ODP Site 663), covering isotopic stages 12 and 11, reveal that deposition of terrigenous OM was higher under past glacial conditions, in correspondence to generally enhanced dust fluxes. Proportions of terrigenous OM, however, never exceed 50% of the total OM according to maceral analyses. Other estimates, recently proposed by Verardo and Ruddiman (1996), are considered to be too high probably for analytical reasons. Palynological records in the Equatorial Atlantic parallel dust records. Increased portions of grass pollen suggest the admixture of C4-plant material under modern and past glacial conditions. It is therefore assumed, as one possible interpetation, that C4-plant debris has an effect on sedimentary d13Corg and might explain differences between isotopic and microscopic quantitative estimates. Using the difference between these two records, we calculate that maximum supply of C4-material remains below 20% of the total OM for the deep modern and past glacial/interglacial Equatorial Atlantic.

Sediments in arctic sea ice - entrainment, characterization and quantification

Sediments in Arctic sea ice are important for erosion and redistribution and consequently a factor for the sediment budget of the Arctic Ocean. The processes leading to the incorporation of sediments into the ice are not understood in detail yet. In the present study, experiments on the incorporation of sediments were therefore conducted in ice tanks of The Hamburg Ship Model Basin (HSVA) in winter 1996/1997, These experiments showed that on average 75 % of the artificial sea-ice sediments were located in the brine-channel system. The sediments were scavenged from the water column by frazil ice. Sediments functioning as a nucleus for the formation of frazil ice were less important for the incorporation. Filtration in grease ice during relatively calm hydrodynamic conditions was probably an effective process to enrich sediments in the ice. Wave fields did not play an important role for the incorporation of sediments into the artificial sea ice. During the expedition TRANSDRIFT III (TDIII, October 1995), different types of natural, newly-formed sea ice (grease ice, nilas and young ice) were sampled in the inner Laptev Sea at the time of freeze-up. The incorporation of sediments took place during calm meteorological conditions then. The characteristics of the clay mineral assemblages of these sedirnents served as references for sea-ice sediments which were sampled from first-year drift ice in the outer Laptev Sea and the adjacent Arctic Ocean during the POLARSTERN expedition ARK-XI/1 (July-September 1995). Based on the clay mineral assemblages, probable incorporation areas for the sedirnents in first-year drift ice could be statistically reconstructed in the inner Laptev Sea (eastern, central, and Western Laptev Sea) as well as in adjacent regions. Comparing the amounts of particulate organic carbon (POC) in sea-ice sediments and in surface sediments from the shelves of potential incorporation areas often reveals higher values in sea-ice sediments (TDIII: 3.6 %DM; ARK-XI/1: 2.3 %DM). This enrichment of POC is probably due to the incorporation process into the sea ice, as could be deducted from maceral analysis and Rock-Eval pyrolysis. Both methods were applied in the present study to particulate organic material (POM) from sea-ice sediments for the first time. It was shown that the POM of the sea-ice sediments from the Laptev Sea and the adjacent Arctic Ocean was dominated by reworked, strongly fragmented, allochthonous (terrigenous) material. This terrigenous component accounted for more than 75 % of all counted macerals. The autochthonous (marine) component was also strongly fragmented, and higher in the sediments from newly-formed sea ice (24 % of all counted macerals) as compared to first-year drift ice (17 % of all counted macerals). Average hydroge indices confirmed this pattern and were in the transition zone between kerogen types II and III (TDIII: 275 mg KW/g POC; ARK-XI/1: 200 mg KW/g POC). The sediment loads quantified in natural sea ice (TDIII: 33.6 mg/l, ARK-XI/1: 49.0 mg/l) indicated that sea-ice sediments are an important factor for the sediment budget in the Laptev Sea. In particular during the incorporation phase in autumn and early winter, about 12 % of the sediment load imported annually by rivers into the Laptev Sea can be incorporated into sea ice and redistributed during calm meteorological conditions. Single entrainment events can incorporate about 35 % of the river input into the sea ice (ca. 9 x 10**6 t) and export it via the Transpolar Drift from the Eurasian shelf to the Fram Strait.