Lignin, phenols, and some chemical elements in aerosols and bottom sediments from the Tropical North Atlantic

A study of composition of biomarkers (lignin and phenols) in aerosols and bottom sediments from the Tropical North Atlantic was carried out. It was shown that organic matter of aerosols was mostly composed of products of terrestrial plants (arboreal fibers, pollen, and spores). Biomarker composition in the aerosols and in the bottom sediments was practically similar, which proved delivery of terrigenous organic matter to the ocean via the atmosphere.

Mineralogy and pyrolysis at DSDP Hole 62-463

A 15-meter sequence of early Aptian organic-matter-rich sediments, cored at Deep Sea Drilling Project Site 463 (western Mid-Pacific Mountains) has been submitted for detailed mineralogical studies (XRD, SEM) and organiccarbon characterization. Although intense diagenesis has obscured the sedimentary record of depositional conditions, the history has been tentatively reconstructed. Through sustained volcanic activity and alteration processes on the archipelago, large amounts of silica were released into the sea water, resulting in a "bloom" of radiolarians. Hard parts settled in large amounts, yielding a hypersiliceous sediment; amorphous silica was diagenetically transformed into chalcedony, opal-CT and clinoptilolite through dissolution and recrystallization. Oxidization of part of the radiolarian soft parts (1) depleted the sea water in dissolved oxygen, allowing the burial of organic matter, and (2) generated carbon dioxide which led to dissolution of most of the calcareous tests. Moderate depositional depth and a high sedimentation rate are though to have prevailed during this episode. An immature stage of evolution is assigned to the studied organic matter, which is of two origins: autochthonous marine material, and allochthonous humic compounds and plant debris. Rhythmic sedimentation characterizes the distribution of the organic matter; each sequence shows (1) an upward progressive increase in organic-carbon content, and (2) an upward enrichment in marine organic matter.

Biomarkers in surface sediments from the Ob and Yenisei estuaries and the southern Kara Sea

Organic-geochemical bulk parameter (Total organic carbon contents, C/N ratios and d13Corg values), biogenic opal and biomarkers (n-alkanes, fatty acids, sterols and amino acids) were determined in surface sediments from the Ob and Yenisei estuaries and the adjacent southern Kara Sea. Maximum TOC contents were determined in both estuaries, reaching up to 3 %. Relatively high C/N ratios around 10, light d13Corg values of -26.5 per mil (Yenisei) and -28 to -28.7 per mil (Ob), and maximum concentrations of long-chain n-alkanes of up to about 10 µg/g Sed clearly show the predominance of terrigenous organic matter in the sediments from the estuaries. Towards the open Kara Sea, all p arameters indicate a decrease in terrigenous organic carbon. Brassicasterol as well as the short-chain n-alkanes parallel this trend, suggesting that these biomarkers are probably also related to a terrigenous (fresh-water phytoplankton) source. Amino acid spectra show characteristic trends from the Yenisei Estuary to the open Kara Sea revealing increasing state of degradation. Sedimentary organic matter in the Yenisei Estuary is relatively less degraded compared to the Ob Estuary and the open Kara Sea.

Gas hydrates of the Gulf of Mexico

Gas hydrates were recovered from eight sites on the Louisiana slope of the Gulf of Mexico. The gas hydrate discoveries ranged in water depths from 530 to 2400 m occurring as small to medium sized (0.5-50 mm) nodules, interspersed layers (1-10 mm thick) or as solid masses (> 150 mm thick). The hydrates have gas:fluid ratios as high as 170:1 at STP, C1/(C2 + C3) ratios ranging from 1.9 to > 1000 and d13C ratios from -43 to -71 per mil. Thermogenic gas hydrates are associated with oil-stained cores containing up to 7% extractable oil exhibiting moderate to severe biodegradation. Biogenic gas hydrates are also associated with elevated bitumen levels (10-700 ppm). All gas hydrate associated cores contain high percentages (up to 65%) of authigenic, isotopically light carbonate. The hydrate-containing cores are associated with seismic "wipeout" zones indicative of gassy sediments. Collapsed structures, diapiric crests, or deep faults on the flanks of diapirs appear to be the sites of the shallow hydrates.

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.

Hydrocarbons, sterols and alkenones at time series station KERFIX

Hydrocarbons, sterols and alkenones were analyzed in samples collected from a 10 month sediment trap time series deployed in the Indian Ocean sector of the Southern Ocean. Fluxes and within-class distributions varied seasonally. During higher mass and organic carbon (OC) flux periods, which occurred in austral summer and fall, fresh marine inputs were predominant. Vertical fluxes were most intense in January, but limited to one week in duration. They were, however, low compared with other oceanic regions. In contrast, low mass and OC flux periods were characterized by a strong unresolved complex mixture (UCM) in the hydrocarbon fraction and a high proportion of stanols as a result of zooplanktonic grazing. Terrigenous inputs were not detectable. The alkenone compositions were consistent with previous data on suspended particles from Antarctic waters. However, UK'37 values diverged from the linear and exponential fits established by Sikes et al. (1997, doi:10.1016/S0016-7037(97)00017-3) in the low temperature range. The seasonal pattern of alkenone production implied that IPT (integrated production temperature) is likely to be strongly imprinted by austral summer and fall SST (sea surface temperature).

Biochemical, geochemical and sedimentological study of ODP Leg 112 samples

Organic-rich diatomaceous muds from Ocean Drilling Program Leg 112 (offshore Peru) are the subject of a comprehensive organic diagenetic study covering the burial interval, <1 to >100 m. The organic matter has been classified in terms of its elemental, biochemical, and geochemical compositions. About 60% of the organic carbon in sediments from <1 m can be attributed to hydrolyzable, biochemical constituents, while at 22 m this figure decreased to 20%. Pyrolysis-gas chromatography and gas chromatography-mass spectrometry chromatograms of these same sediments contain mainly hydrocarbons and nitrogenous compounds, with low amounts of other heteroatomic compounds, even though the total organic matter is rich in oxygen (about 35 atoms per 100 carbon atoms) and sulfur (1 to 5 atoms per 100 C atoms). Overall, the organic matter in these sediments, even at these shallow depths and young ages, has many of the geochemical features of far more deeply buried sediments, providing further strong evidence for the claim that "kerogen-formation" is a very early diagenetic process.

Geochemistry and petrography of organic matter at DSDP Site 93-603

A series of 22 sediment samples of Cretaceous and Cenozoic age from DSDP Holes 603, 603B, and 603C at the continental rise off the northeastern American coast near Cape Hatteras was 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. An abundance of terrigenous organic matter, including larger coal particles (almost exclusively consisting of huminite/vitrinite macerals), is the dominant characteristic of the organofacies types at Site 603. Marine organic matter, mostly structurally degraded and in the form of fecal pellets, was preserved in the Valanginian laminated marls and in Cenomanian black claystone turbidites. Long-chain nalkanes reflect the terrigenous imprint in the nonaromatic hydrocarbon fractions, whereas a second maximum at lower carbon numbers in most cases is caused by the presence of more mature recycled organic matter. Abundant isoprenoid and steroid hydrocarbons were found in sediments containing mainly marine organic matter, whereas hopanoids reflect the ubiquitous microbial activity. The organic matter in the Site 603 sediments, in so far as it is not recycled, is thermally immature.

n-Alkanes and lignin in bottom sediments of the West European Basin (area of the battleship Bismark wreck site)

Three bottom sediment cores were collected from the top, slope, and foot of a small topographic high located near the West European continental rise within the Porcupine abyssal plain at the battleship Bismark wreck site. Using high-efficient gas chromatography technique we determined content and examined molecular composition of n-alkane fraction of hydrocarbons and phenol compounds of lignin. n-Alkane and phenol concentrations in bottom sediments of all three cores were low both in values per unit mass of sediments and in organic matter composition that is typical for pelagic deposits of the World Ocean. They vary from 0.07 to 2.01 µg/g of dry sediment and from 0.0001 to 0.01% of TOC; phenol ranges are from 1.43 to 11.1 µg/g and from 0.03 to 0.6%. Non-uniform supply of terrigenous matter to the bottom under conditions of changes in sedimentation environment in different geological epochs is the principal reason for significant variations in n-alkane and lignin concentrations with depth in the cores. Lignin and its derivatives make the main contribution to formation of organic matter composition of the region in study. With respect to n-alkane and lignin concentrations organic matter of deposits of the West European Basin is composed of remains of higher plants and of autochtonous organic matter of marine flora; they have mixed terrigenous-autochtonous (terrigenous-planktonogenic) origin.

Geochemistry of Albian to Santonian black shale sequences on the Demerara Rise, South American margin

Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian-Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, d13Corg values lie mostly between -30 per mil and -27 per mil, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C3 land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low d13Corg values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian-Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.

Organic chemistry of sediments from the Tyrrhenian Sea

Thirty sediment samples from Tortonian to Pleistocene age of five ODP locations (Holes 650A, 651A, and 652A, and Sites 654 and 655) in the Marsili Basin, Vavilov Basin, and Sardinia Margin (Tyrrhenian Sea) were studied by organic geochemical methods including total organic carbon determination, Rock-Eval pyrolysis, bitumen extraction, pyrolysis-gas chromatography, and organic petrography. Six organic facies, including open ocean anoxia with variable terrestrial input, oxic open ocean, oxic tidal flat, mildly oxic lagoon, and anoxic lacustrine algal-bacterial mat environments, have been recognized in these sediments. The sediments below 500 m in Sardinia Margin are mature for significant hydrocarbon generation. Possible mature source-rock (Type I and IIB/III kerogen) and migrated bitumen occur in the deeper part of the section in Vavilov Basin and Sardinia Margin sediments. Sporadic sapropel formation observed in the studied Pliocene-Pleistocene sediment section is probably controlled by organic productivity due to nutrient supply by the rivers and terrestrial input associated with open ocean anoxia or anoxia caused by the material balance between rate of organic matter supplied by turbidites and organic matter consumption. Pliocene and Pleistocene sapropels are mostly immature and lie within Type II-III (precisely as IIA-IIB and IIB source rocks) kerogen maturation path.

Water chemistry, and pigments and geochemistry of sediments from northern Victoria Land lakes

Total concentrations of algal pigments, organic C, C, N, P and S were determined in surface sediments from the littoral zone of 21 lakes in ice-free areas of northern Victoria Land (Antarctica) with different climatic and environmental conditions. Concentrations of major ions and nutrients were also determined in water samples from the same lakes. The latter samples had extremely variable chemical compositions; however, all the lakes resulted oligotrophic. Pigment concentrations in surface sediments were comparable to those reported for other Antarctic lakes and lower than those in oligotrophic lakes at lower latitudes. Cyanophyta, Chlorophyta and Bacillariophyta were the main taxa identified. These taxa correspond to those reported in previous microscopy-based studies on Antarctic phytoplankton and phytobenthos. Discriminant Function Analysis and Canonical Correspondence Analysis of data indicate that the distribution of pigments in these Victoria Land lakes depends mainly on their geographical location (particularly the distance from the sea) and nutrient status.

Chemistry of organic matter of glacial and Cretaceous sediments from the Prydz Bay

Organic matter in Miocene glacial sediments in Hole 739C on the Antarctic Shelf represents erosional recycled continental material. Various indications of maturity in bulk organic matter, kerogens, and extracts imply that an exposed section of mature organic carbon-rich material was present during the Miocene. Based on biomarker, n-alkane, and kerogen analysis, a massive diamictite of early Eocene/Oligocene age at Hole 739C contains immature organic matter. Visual and pyrolysis analyses of the kerogens suggest a predominance of terrestrial organic matter in all samples from Hole 739C. A reversal of thermal maturities, i.e., more-mature overlying less-mature sections, may be related to redeposition generated from glacial erosion. Siliciclastic fluviatile sediments of Lower Cretaceous age from Hole 741A were analyzed. The organic matter from this hole contains immature aliphatic and aromatic biomarkers as well as a suite of odd carbon number-dominated nalkanes. Visual examination and pyrolysis analysis of the kerogen suggests that predominantly immature terrestrial organic matter is present at Hole 741A. The similarities between Hole 739C Unit V and Hole 741A suggest that the source of the organic matter in the glacial sediments in Unit V at Hole 739C could be Cretaceous in age and similar to sediments sampled at Hole 741A in Prydz Bay.