Highly dealkylated copper and nickel etioporpyfrins in marine sediments

Copper porphyrins have been recognized as natural constituents of marine sediments only within the past 5 years (Palmer and Baker, 1978, Science201, 49-51). In that report it was suggested that these pigments may derive from and be markers for oxidized terrestrial organic matter redeposited in the marine environment. In the present study we describe the distribution of copper porphyrins in sediments from several north Pacific and Gulf of California DSDP/IPQD sites (Legs 56,63,64). These allochthonous pigments have now been found to be accompanied by identical arrays of highly dealkylated nickel etioporphyrins. Evaluation of data from this and past studies clearly reveals that there is a strong carbon-number distribution similarity betweeen coincident Cu and Ni etioporphyrins. This homology match is taken as reflecting a common source for the tetrapyrrole ligands of this population of Cu and Ni chelates. Predepositional generation of these highly dealkylated etioporphyrins is concluded from the occurrence of these pigments in sediments continuing essentially all stages of in situ chlorophyll diagenesis (cf. Baker and Louda, 1983). That is, their presence is not regulated by the in situ diagenetic continuum. Thus, the highly dealkylated Cu and Ni etioporphyrins represent an 'allochthonous' background over which 'autochthonous' (viz. marine produced) chlorophyll derivatives are deposited and are undergoing in situ diagenesis.

Concentration of organic compounds in aerosols and surface waters of the East Atlantic and Antarctic

The data on content and composition of lipids and aliphatic hydrocarbons (HC) in aerosols and surface waters obtained during the spring-summer periods of 2001 and 2003 along the vessel route from the North Sea to the Antarctic and backwards are presented. It was shown that the distribution of organic compounds is caused by influence of zonal supply of eolian matter from land, anthropogenic, and marine autochtonous sources. Concentrations of organic compounds in the aerosols varied from 0.22 to 13.04 ng/m**3 for lipids and from 0.04 to 7.03 ng/m**3 for aliphatic HC; in surface waters, it from 9 to 84 and from 1 to 53 µg/l, respectively. There is correlation between fluxes of lithogenic fraction of the aerosols, HC, and lipids. Growth of productivity in the aquatic area increases levels of the HC in the surface waters but to a lower degree than HC supply with oil contamination.

Composition of organic matter in suspended matter and bottom sediments of the southeastern Baltic Sea

Data on contents and compositions of hydrocarbons (HCs)-aliphatic (AHCs) and polycyclic aromatic (PAHs) are provided in comparison with contents of total organic carbon (Corg), lipids in suspended matter, and Corg in bottom sediments. Particular attention is paid to distribution of HCs in the area of the Kravtsov oil field. It is established that concentrations of AHCs in water are governed by concentrations of suspended matter and elevated AHC concentrations are confined to coastal areas. In the area of D-6 platform sandy bottom sediments are notable for great variability of HC concentrations, both laterally and from year to year. In summer of 2010 average content of AHCs was 40 ppm (19% of Corg) and that of PAHs was 0.023 ppm. Natural seepage from sediment mass is considered to be a source of HCs along with oil contamination.

Lipid biomarkers in urface sediments of the Southeast Atlantic

Surface sediments from the eastern South Atlantic were investigated for their lipid biomarker contents and bulk organic geochemical characteristics to identify sources, transport pathways and preservation processes of organic components. The sediments cover a wide range of depositional settings with large differences in mass accumulation rates. The highest marine organic carbon (OC) contributions are detected along the coast, especially underlying the Benguela upwelling system. Terrigenous OC contributions are highest in the Congo deep-sea fan. Lipid biomarker fluxes are significantly correlated to the extent of oxygen exposure in the sediment. Normalization to total organic carbon (TOC) contents enabled the characterization of regional lipid biomarker production and transport mechanisms. Principal component analyses revealed five distinct groups of characteristic molecular and bulk organic geochemical parameters. Combined with information on lipid sources, the main controlling mechanisms of the spatial lipid distributions in the surface sediments are defined, indicating marine productivity related to river-induced mixing and oceanic upwelling, wind-driven deep upwelling, river-supply of terrigenous organic material, shallow coastal upwelling and eolian supply of plant-waxes.

Distribution and stable isotopic compositions of hydrogen and carbon of plant-wax derived n-C29 and -C31 alkanes in terrestrial, coastal and offshore surface sediments

Reconstructing terrestrial water budgets is of prime importance for understanding past climate and environment. To shed more light on how plant-wax derived n-alkanes may be used for this purpose we investigated the distribution and stable isotopic compositions of hydrogen (dD) and carbon (d13C) of plant-wax derived n-C29 and -C31 alkanes in terrestrial, coastal and offshore surface sediments in relation to hydrology along a NW-SE transect east of the Italian Apennines from the Po River to the Eastern Gulf of Taranto. The plant wax average chain length increases southward and may relate to increasing temperature and/or aridity. The plant wax dD of the terrestrial and coastal samples also increases southward and mainly reflects changes in the dD of precipitation. The d13C of plant waxes is primarily interpreted in terms of C3 vegetation changes rather than varying contributions by C4 plants. The plant wax d13C-dD composition of the Po River and Apennine rivers differs considerably from that in southern Italy, and suggests a mainly southern source for plant waxes in marine sediments of the Gulf of Taranto. This calibration provides a basis for the reconstruction of past changes in the Italian water balance and n-alkane source areas.

Bitumen and n-alkanes in organic matter from sedimentary rocks sampled in DSDP Holes 47-397A and 47-398

A study of samples from DSDP Leg 47 shows that transformation of organic matter in deep sea sediments is completly analogous to evolution of organic matter in sedimentary sequences on continents and depends on the same factors. Crucial among these factors are: genesis of organic matter, nature of its diagenetic changes, and current stage of catagenesis.

Documentation of sediment cores from the Great Meteor Seamount, North Atlantic

Sedimentological and biostratigraphic investigations of 15 cores (total length: 88 m) from the vicinity of Great Meteor seamount (about 30° N, 28° W) showed that the calcareous ooze are asymmetrically distributed around the seamount and vertically differentiated into two intervals. East and west of the seampunt, the upper "A"-interval is characterized by yellowish-brown sediment colors and bioturbation; ash layers and diatoms are restricted to the eastern cores. On both seamount flanks, the sediment of the lower "B"-interval are white and very rich in CaCO3 with a major fine silt (2-16 µ) mode (mainly coccoliths). Lamination, manganese micronodules, Tertiary foraminifera and discoasters, and small limestone and basalt fragments are typical of the "B"-interval of the eastern cores only. The sediments contain abundant displaced material which was reworked from the upper parts of the seamount. The sedimentation around the seamount is strongly influenced by the kind of displaced material and the intensity of its differentiated dispersal: the sedimentation rates are generally higher on the east than on the west flank /e.g. in "B": 0.9 cm/1000 y in the W; 3.1 cm/1000 y in the E), and lower for the "A" than for the "B"-interval. The lamination is explained by the combination of increased sedimentation rates with a strong input of material poor in organic carbon producing a hostile environment for benthic life. The CaCO3 content of the core is highly influenced by the proportion of displaced bigenous carbonate material (mainly coccoliths). The genuine in-situ conditions of the dissolution facies are only reflected by the minimum CaCO3 values of the cores (CCD = about 5,500 m; first bend in dissolution curve = 4,000 m; ACD = about 3,400 m). The preservation of the total foraminiferal association depends on the proportions of in-situ versus displaced specimens. In greater water depths (stronger dissolution), for example, the preservation can be improved by the admixture of relatively well preserved displaced foraminifera. Carbonate cementation and the formation of manganese micronodules are restricted to microenvironments with locally increased organic carbon contents (e.g. pellets; foraminifera). The ash layers consist of redeposited, silicic volcanic glass of trachytic composition and Mio-Pliocene age; possibly, they can be derived from the upper part of the seamount. Siliceous organisms, especially diatoms, are frequent close to the ash layers and probably also redeposited. Their preservation was favoured by the increase of the SiO2 content in the pore water caused by the silicic volcanic glass. The cores were biostraftsraphically subdivided with the aid of planktonic foraminifera and partly alsococcoliths. In most cases, the biostratigraphically determined cold- and warm sections could be correlated from core to core. Almost all cores do not penetrate the Late Pleistocene. All Tertiary fossils are reworked. In general, the warm/cold boundary W2/C2 corresponds with the lithostratigraphic A/B boundray. Benthonic foraminifera indicate the original site deposition of the displaced material (summit plateau or flanks of the seamount). The asymmetric distribution of the sediments around the seamount east and west of the NE-directed antarctic bottom current (AABW) is explained by the distortion of the streamlines by the Coriolis force; by this process the current velocity is increased west of the seamount and decreased east of it. The different proportion of displaced material within the "A" and "B" interval is explained by changes of the intensity of the oceanic circulation. At the time of "B" the flow of the AABW around the seamount was stronger than during "A"; this can be inferred from the presence of characteristic benthonic foraminifera. The increased oceanic circulation implies an enhanced differentiation of the current velocities, and by that, also of the sedimentation rates, and intensifies the winnowed sediment material was transported downslope by turbid layers into the deep-sea, incorporated into the current system of the AABW, and asymmetrically deposited around the seamount.