Geochemistry of labile organic matter in sediments and interstitial waters of ODP Sites 107-651 and 107-653

Sediment and interstitial water from Sites 651 and 653 (ODP Leg 107) were investigated by organic geochemical methods to characterize labile organic compound classes (amino compounds and carbohydrates) and to evaluate their progressive diagenetic and thermal degradation in deep-sea sediments. Downhole distribution of dissolved organic carbon (DOC) appears related to redox zones associated with bacterial activity and of diagenetic recrystallization of biogenic tests and not so much to organic matter concentrations in ambient sediments. DOC ranges from 250 to 8300 µmol/L (3-100.1 ppm). Amino acids contribute 10%-0.3% of DOC; carbohydrates range from 78 to 5 µmol/L. Rate of degradation of amino acids by thermal effects and/or bacterial activity at both sites (significantly different in sedimentation rates: average 41 cm/1000 yr in the top 300 m at Site 651, average 3.9 cm/1000 yr in the Pliocene/Quaternary sequence at Site 653 to 220 mbsf) is more dependent on exposure time rather than on the depth within the sediment column. Variability in neutral, acidic, and basic amino acid fractions of total amino acids (with a range of 1.1-0.02 µmol/g sediment; up to 2.5% of organic carbon) varies with carbonate content and by differences in thermal stability of amino acids. Distribution patterns of monosaccharides are interpreted to result from differences in organic matter sources, sedimentation rates, and the degree of organic matter decomposition prior to and subsequent to burial. Total particulate carbohydrates range from 1.82 to 0.21 µmol/g sediment and contribute about 8% to the sedimentary organic matter. Investigation of trace metals in the interstitial waters did not show any correlation of either DOC, amino compounds, or carbohydrates.

Total organic carbon, metal concentrations and metal and aluminium ratios in bulk sediment from the ODP sample 169-1033B-4H-4,54-74

Holocene laminated sediments in Saanich Inlet, British Columbia, are interrupted by frequent, non-laminated, massive layers. These layers may be debris flows released by earthquakes or bioturbated sediments deposited during periods of relatively high bottom water oxygen concentration and/or low surface productivity, or both. We determined the organic carbon content and the concentration of a suite of redox-sensitive metals in bulk sediments at approximately 1-cm resolution across a laminated-massive-laminated interval (ODP Leg 169S Sample 1033B-4H-4,54-74), to determine the redox conditions under which the massive layer was deposited. Our results indicate that this massive interval was deposited under anoxic bottom waters. Manganese/Al ratios are consistently low throughout the massive section, while Mo/Al, Cd/Al, Re/Al, and U/Al ratios are enriched relative to their metal/Al ratios in detrital material (represented by Cowichan River suspended sediments). The concentration of organic carbon in the lower portion of the massive layer is higher than in the upper portion, which has a concentration similar to that in the overlying and underlying laminated sediments. Well-defined peaks in Mo/Al, Cd/Al, and Re/Al and a broad peak in U/Al occur in the lower portion of the massive layer. The positions of the Cd/Al, Re/Al, and Mo/Al peaks, as well as the increase in organic carbon content with depth in the massive layer, are best explained by a process of diagenetic redistribution of metals that occurred after the massive layer was emplaced.

Organic carbon, reduced sulfur, and iron in Miocene to Holocene sediments from the Oman and Beguela upwelling systems

We examined sediments from Neogene and Quaternary sections of the Benguela and Oman upwelling systems (DSDP Site 532, ODP Sites 723 and 722) to determine environmental and geochemical factors which control and limit pyrite formation in organic-carbon-rich marine sediments. Those samples from the upwelling sites, which contained low to moderate concentrations of total organic carbon (0.7%-3%), had C/S ratios typical of normal marine sediments, i.e., around 2.8. In these sediments, TOC availability probably limited pyrite formation. Results that do not conform with accepted models were found for the sediments high in TOC (3^0-12.4%). The organic matter was of marine origin and contained considerable pyrolytic hydrocarbons, a fact that we take as a sign of low degradation, yet significant concentrations of dissolved sulfate coexisted with it (> 5 mmol/L in the case of Sites 532 and 723). Detrital iron was probably not limiting in either case, because the degree of pyritization was always less than 0.65. Therefore, controls on sulfate reduction and pyrite formation in the organic matter-rich sediments do not appear to conform simply to generally accepted diagenetic models. The data from these thermally immature, old, and organic-rich marine sediments imply that (1) the total reduced sulfur content of organic-rich marine upwelling sediments rarely exceeds an approximate boundary of 1.5% by weight, (2) the C/S ratio of these sediments is not constant and usually much higher than the empirical values proposed for marine sediments. We conclude that sedimentary pyrite formation in upwelling sediments is limited by an as yet unknown factor, and that caution is advised in using C/S ratios and C vs. S diagrams in paleoenvironmental reconstructions for organic-rich sediments.

Organic compounds in surface sediments from the Pakistan continental margin

In order to assess whether the oxygen-minimum zone (OMZ) in the Arabian sea has an effect on the preservation and composition of organic matter in surface sediments we investigated samples from three different transects on the Pakistan continental margin across the OMZ. In addition to determining the total amount of organic carbon (TOC), we analyzed the extractable lipids by gas chromatography, combined gas chromatography/mass spectrometry, and compound-specific stable carbon isotope measurements. The extractable lipids are dominated by marine organic matter as indicated by the abundance of lipids typical of marine biota and by the bulk and molecular isotopic composition. Sediments from within the OMZ are enriched in organic carbon and in several extractable lipids (i.e. phytol, n-alcohols, total sterols, n-C35 alkane) relative to stations above and below this zone. Other lipid concentrations, such as those of total n-fatty acids and total n-alkanes fail to show any relation to the OMZ. Only a weak correlation of TOC with mineral surface area was found in sediments deposited within the OMZ. In contrast, sediments from outside the OMZ do not show any relationship between TOC and surface area. Among the extractable lipids, only the n-alkane concentration is highly correlated with surface area in sediments from the Hab and Makran transects. In sediments from outside the OMZ, the phytol and sterol concentrations are also weakly correlated with mineral surface area. The depositional environment of the Indus Fan offers the best conditions for an enhanced preservation of organic matter. The OMZ, together with the undisturbed sedimentation at moderate rates, seems to be mainly responsible for the high TOC values in this area. Overall, the type of organic matter and its lability toward oxic degradation, the mineral surface area, the mineral composition, and possibly the secondary productivity by (sedimentary) bacteria also appear to have an influence on organic matter accumulation and composition.

Uranium in Black Sea bottom sediments

Results of uranium content determinations in 76 samples of surface layer bottom sediments, from sediment cores, and deep-sea drilling cores are reported. These data confirm previously established regularities of uranium distribution in Black Sea bottom sediments. The main factors of its concentration are hydrochemical features of the hydrogen sulfide enrichment zone and enrichment of deep-sea sediments in organic matter resulting to increase (4-6 times) of uranium content in comparison with its average content in sedimentary rocks.

Organic carbon accumulation in the South Atlantic Ocean

A compilation of 1118 surface sediment samples from the South Atlantic was used to map modern seafloor distribution of organic carbon content in this ocean basin. Using new data on Holocene sedimentation rates, we estimated the annual organic carbon accumulation in the pelagic realm (>3000 m water depth) to be approximately 1.8*10**12 g C/year. In the sediments underlying the divergence zone in the Eastern Equatorial Atlantic (EEA), only small amounts of organic carbon accumulate in spite of the high surface water productivity observed in that area. This implies that in the Eastern Equatorial Atlantic, organic carbon accumulation is strongly reduced by efficient degradation of organic matter prior to its burial. During the Last Glacial Maximum (LGM), accumulation of organic carbon was higher than during the mid-Holocene along the continental margins of Africa and South America (Brazil) as well as in the equatorial region. In the Eastern Equatorial Atlantic in particular, large relative differences between LGM and mid-Holocene accumulation rates are found. This is probably to a great extent due to better preservation of organic matter related to changes in bottom water circulation and not just a result of strongly enhanced export productivity during the glacial period. On average, a two- to three-fold increase in organic carbon accumulation during the LGM compared to mid-Holocene conditions can be deduced from our cores. However, for the deep-sea sediments this cannot be solely attributed to a glacial productivity increase, as changes in South Atlantic deep-water circulation seem to result in better organic carbon preservation during the LGM.

(Table 1) Organic carbon, hydrogen and oxygen index and hydrocarbons at DSDP Hole 93-603B

C2-C8 hydrocarbon concentrations (about 35 compounds identified, including saturated, aromatic, and olefinic compounds) from 27 shipboard-sealed, deep-frozen core samples of DSDP Hole 603B off the east coast of North America were determined by a gas-stripping/thermovaporization method. Total yields representing the hydrocarbons dissolved in the pore water and adsorbed on the mineral surfaces of the sediments vary from 22 to 2400 ng/g of dryweight sediment. Highest yields are measured in the two black shale samples of Core 603B-34 (hydrogen index of 360 and 320 mg/g Corg, respectively). In organic-carbon-normalized units these samples have hydrocarbon contents of 12,700 and 21,500 ng/g Corg, respectively, indicating the immaturity of their kerogens. Unusually high organic-carbonnormalized yields are associated with samples that are extremely lean in organic carbon. It is most likely that they are enriched by small amounts of migrated light hydrocarbons. This applies even to those samples with high organic-carbon contents (1.3-2.2%) of Sections 603B-28-4, 603B-29-1, 603B-49-2, and 603B-49-3, because they have an extremely low hydrocarbon potential (hydrogen index between 40 and 60 mg/g Corg). Nearly all samples were found to be contaminated by varying amounts of acetone that is used routinely in large quantities on board ship during core-cutting procedures. Therefore, 48 samples from the original set of 75 collected had to be excluded from the present study.

(Table T2) Relative signal intensity of intact polar lipids in sediments from ODP Sites 207-1257 and 207-1258

We report results from the analysis of intact polar lipids (IPLs) in sediments from Ocean Drilling Program Sites 1257 and 1258. IPLs, constituting the cell membranes of living organisms, were detected in organic-lean sediments but not in underlying organic-rich black shales. Microbial activity in organic-lean sediments is likely due to sulfate-dependent oxidation of methane whereas difficulties detecting IPLs in black shales are interpreted to result from unfavorable signal-to-noise ratios due to low cell concentrations in combination with extremely high analytical noise created by uncharacterized organic matrix. IPLs found are consistent with a low-diversity community of archaea and bacteria. The concentrations of IPLs are more than one order of magnitude lower than those in Neogene deep subsurface sediments at the Peruvian margin, suggestive of significantly lower cell concentrations in Demerara Rise. This finding is consistent with inferred low rates of subsurface microbial activity.

Soil organic carbon storage and soil properties for 50 soil profiles in the Lena River Delta including land form description and map

To project the future development of the soil organic carbon (SOC) storage in permafrost environments, the spatial and vertical distribution of key soil properties and their landscape controls needs to be understood. This article reports findings from the Arctic Lena River Delta where we sampled 50 soil pedons. These were classified according to the U.S.D.A. Soil Taxonomy and fall mostly into the Gelisol soil order used for permafrost-affected soils. Soil profiles have been sampled for the active layer (mean depth 58±10 cm) and the upper permafrost to one meter depth. We analyze SOC stocks and key soil properties, i.e. C%, N%, C/N, bulk density, visible ice and water content. These are compared for different landscape groupings of pedons according to geomorphology, soil and land cover and for different vertical depth increments. High vertical resolution plots are used to understand soil development. These show that SOC storage can be highly variable with depth. We recommend the treatment of permafrost-affected soils according to subdivisions into: the surface organic layer, mineral subsoil in the active layer, organic enriched cryoturbated or buried horizons and the mineral subsoil in the permafrost. The major geomorphological units of a subregion of the Lena River Delta were mapped with a land form classification using a data-fusion approach of optical satellite imagery and digital elevation data to upscale SOC storage. Landscape mean SOC storage is estimated to 19.2±2.0 kg C/m**2. Our results show that the geomorphological setting explains more soil variability than soil taxonomy classes or vegetation cover. The soils from the oldest, Pleistocene aged, unit of the delta store the highest amount of SOC per m**2 followed by the Holocene river terrace. The Pleistocene terrace affected by thermal-degradation, the recent floodplain and bare alluvial sediments store considerably less SOC in descending order.