Organic geochemistry of deep sea sediments from the Nankai Trough and the Southwest Japan forearc region

Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m**2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

(Table 1) Turbidity, temperature, and salinity in the hydrothermal plume and background waters above the northern part of the Mohn's Ridge at Station AMK36-3573-5

In July 1995 geological and biological studies in the axial zone of the northern part of the Mohn's Ridge (72°20'N) were carried out during Cruise 36 of R/V Akademik Mstislav Keldysh. Slopes of the neovolcanic zone, as well as a caldera on its crest were investigated with use of deep-sea manned submersibles Mir, geological and biological samples were also collected. Use of the Rosette sounding complex provided recognition of several major hydrothermal plumes. Bottom sediments of the marginal depression are enriched in metals characteristic for hydrothermal metalliferous sediments. Thus, a new unknown hydrothermal field was found.

Pore water methane characteristics and sulphate reduction rates of ODP Leg 164 sediments

Anaerobic methane oxidation (AMO) was characterized in sediment cores from the Blake Ridge collected during Ocean Drilling Program (ODP) Leg 164. Three independent lines of evidence support the occurrence and scale of AMO at Sites 994 and 995. First, concentration depth profiles of methane from Hole 995B exhibit a region of upward concavity suggestive of methane consumption. Diagenetic modeling of the concentration profile indicates a 1.85-m-thick zone of AMO centered at 21.22 mbsf, with a peak rate of 12.4 nM/d. Second, subsurface maxima in tracer-based sulfate reduction rates from Holes 994B and 995B were observed at depths that coincide with the model-predicted AMO zone. The subsurface zone of sulfate reduction was 2 m thick and had a depth integrated rate that compared favorably to that of AMO (1.3 vs. 1.1 nmol/cm**2/d, respectively). These features suggest close coupling of AMO and sulfate reduction in the Blake Ridge sediments. Third, measured d13CH4 values are lightest at the point of peak model-predicted methane oxidation and become increasingly 13C-enriched with decreasing sediment depth, consistent with kinetic isotope fractionation during bacterially mediated methane oxidation. The isotopic data predict a somewhat (60 cm) shallower maximum depth of methane oxidation than do the model and sulfate reduction data.

Composition of surface layer bottom sediments from the Kem' River estuary, White Sea

Based on grain-size, mineralogical and chemical analyses of samples collected in cruises of R/V Ekolog (Institute of Northern Water Problems, Karelian Research Centre of RAS, Petrozavodsk) in 2001 and 2003 regularities of chemical element distribution in surface layer bottom sediments of the Kem' River Estuary in the White Sea were studied. For some toxic elements labile and refractory forms were determined. Correlation analysis was carried out and ratios Me/Al were calculated as proxies of terrigenous contribution. Distribution of such elements as Fe, Mn, Zn, Cr, Ti was revealed to be influenced by natural factors, mainly by grain size composition of bottom sediments. These metals have a tendency for accumulation in fine-grained sediments with elevated organic carbon contents. Distribution of Ni is different from one of Fe, Mn, Zn, Cr, Ti. An assumption was made that these distinctions were caused by anthropogenic influence.

Petrography and geochemistry of organic matter in Triassic and Cretaceous sediments from the Wombat and Exmouth Plateau

Triassic (Carnian-Rhaetian) continental margin sediments from the Wombat Plateau off northwest Australia (Sites 759, 760, 761, and 764) contain mainly detrital organic matter of terrestrial higher plant origin. Although deposited in a nearshore deltaic environment, little liptinitic material was preserved. The dominant vitrinites and inertinites are hydrogen-lean, and the small quantities of extractable bitumen contain w-alkanes and bacterial hopanoid hydrocarbons as the most dominant single gas-chromatography-amenable compounds. Lower Cretaceous sediments on the central Exmouth Plateau (Sites 762 and 763) farther south in general have an organic matter composition similar to that in the Wombat Plateau sediments with the exception of a smaller particle size of vitrinites and inertinites, indicating more distal transport and probably deposition in deeper water. Nevertheless, organic matter preservation is slightly better than in the Triassic sediments. Long-chain fatty acids, as well as aliphatic ketones and alcohols, are common constituents in the Lower Cretaceous sediments in addition to n-alkanes and hopanoid hydrocarbons. Thin, black shale layers at the Cenomanian/Turonian boundary, although present at several sites (Sites 762 and 763 on the Exmouth Plateau, Site 765 in the Argo Abyssal Plain, and Site 766 on the continental margin of the Gascoyne Abyssal Plain), are particularly enriched in organic matter only at Site 763 (up to 26%). These organic-matter-rich layers contain mainly bituminite of probable fecal-pellet origin. Considering the high organic carbon content, the moderate hydrogen indices of 350-450 milligrams of hydrocarbon-type material per gram of Corg, the maceral composition, and the low sedimentation rates in the middle Cretaceous, we suggest that these black shales were accumulated in an area of oxygen-depleted bottom-water mass (oceanwide reduced circulation?) underlying an oxygen-rich water column (in which most of the primary biomass other than fecal pellets is destroyed) and a zone of relatively high bioproductivity. Differences in organic matter accumulation at the Cenomanian/Turonian boundary at different sites off northwest Australia are ascribed to regional variations in primary bioproductivity.

Mineral and chemical compositions of authigenic carbonates from the northern Deryugin Basin, Sea of Okhotsk

Mineral and chemical compositions of authigenic carbonates are studied by several methods in a sediment core collected in the axial zone of the Deryugin riftogenic basin. Manganese carbonates (kutnahorite, rhodochrosite) associated with manganiferous calcite, manganiferous pyrite, and nontronite are firstly identified in the Sea of Okhotsk. Manganese carbonates in Holocene diatomaceous ooze were presumably formed due to diagenetic transformation of sedimentary manganese hydroxides, organic matter, and biogenic silica, while those found in the underlying turbidites precipitated owing to the intermittent influx of endogenic fluids migrating along sand interbeds.

Geochemistry and isotopic ratios of samples obtained during R/V Akademik Nikolaj Strakhov cruise ANS24

New petrological and geochemical data were obtained for basalts recovered during cruise 24 of the R/V "Akademik Nikolay Strakhov" in 2006. These results significantly contributed to the understanding of the formation of tholeiitic magmatism at the northern end of the Knipovich Ridge of the Polar Atlantic. Dredging was performed for the first time both in the rift valley and on the flanks of the ridge. It showed that the conditions of magmatism have not changed since at least 10 Ma. The basalts correspond to slightly enriched tholeiites, whose primary melts were derived at the shallowest levels and were enriched in Na and depleted in Fe (Na-TOR type). The most enriched basalts are typical of the earlier stages of the opening and were found on the flanks of the ridge in its northernmost part. Variations in the ratios of Sr, Nd, and Pb isotopes and lithophile elements allowed us to conclude that the primary melts generated beneath the spreading zone of the Knipovich Ridge were modified by the addition of the enriched component that was present both in the Neogene and Quaternary basalts of Spitsbergen Island. Compared with the primitive mantle, the extruding magmas were characterized by positive Nb and Zr anomalies and a negative Th anomaly. The formation of primary melts involved melting of the metasomatized depleted mantle reservoir that appeared during the early stages of opening of the Norwegian-Greenland Basin and transformation of the paleo-Spitsbergen Fault into the Knipovich spreading ridge, which was accompanied by magmatism in western Spitsbergen during its separation from the northern part of Greenland.

Free and dissolved gases in the area of the Calypso hydrothermal vent, Bay of Plenty, New Zealand

Gas composition and hydrochemistry of bottom waters of the Bay of Plenty in the hydrothermally active zone of the Pacific island arc are investigated. Methane content in underwater vents is an order of magnitude greater than that in volcanic exhalations on the land. Salinity, pH, total content of CO2, its partial pressure, and silica content also differ. Correlations between gas parameters, hydrochemical parameters, and biological and microbiological parameters are identified.

(Table 2) Distribution of alkenone unsaturation index UK37 of the eastern North Atlantic

This paper reports the concentrations and within-class distributions of long-chain alkenones and alkyl alkenoates in the surface waters (0-50 m) of the eastern North Atlantic, and correlates their abundance and distribution with those of source organisms and with water temperature and other environmental variables. We collected these samples of >0.8 µm particulate material from the euphotic zone along the JGOFS 20°W longitude transect, from 61°N to 24°N, during seven cruises of the UK-JGOFS Biogeochemical Ocean Flux Study (BOFS) in 1989-1991; the biogeographical range of our 53 samples extends from the cold (<10°C), nutrient-rich and highly productive subarctic waters of the Iceland Basin to the warm (>25°C) oligotrophic subtropical waters off Africa. Surface water concentrations of total alkenone and alkenoates ranged from <50 ng/l in oligotrophic waters below 40°N to 2000-4500 ng/l in high latitude E. huxleyi blooms, and were well correlated with E. huxleyi cell densities, supporting the assumption that E. huxleyi is the predominant source of these compounds in the present day North Atlantic. The within-class distribution of the C37 and C38 alkenones and C36 alkenoates varied strongly as a function of temperature, and was largely unaffected by nutrient concentration, bloom status and other surface water properties. The biosynthetic response of the source organisms to growth temperature differed between the cold (<16°C) waters above 47°N and the warmer waters to the south. In cold (<16°C) waters above 47°N, the relative amounts of alkenoates and C38 alkenones synthesized was a strong function of growth temperature, while the unsaturation ratio of the alkenones (C37 and C38) was uncorrelated with temperature. Conversely, in warm (>16°C) waters below 47°N, the relative proportions of alkenoates and alkenones synthesized remained constant with increasing temperature while the unsaturation ratios of the C37 and C38 methyl alkenones (Uk37 and Uk38Me, respectively) increased linearly. The fitted regressions of Uk37 and Uk38Me versus temperature for waters >16°C were both highly significant (r**2 > 0.96) and had identical slopes (0.057) that were 50% higher than the slope (0.034) of the temperature calibration of Uk37 reported by Prahl and Wakeham (1987; doi:10.1038/330367a0) over the same temperature range. These observations suggest either a physiological adjustment in biochemical response to growth temperature above a 16-17°C threshold and/or variation between different E. huxleyi strains and/or related species inhabiting the cold and warm water regions of the eastern North Atlantic. Using our North Atlantic data set, we have produced multivariate temperature calibrations incorporating all major features of the alkenone and alkenoate data set. Predicted temperatures using multivariate calibrations are largely unbiased, with a standard error of approximately ±1°C over the entire data range. In contrast, simpler calibration models cannot adequately incorporate regional diversity and nonlinear trends with temperature. Our results indicate that calibrations based upon single variables, such as Uk37, can be strongly biased by unknown systematic errors arising from natural variability in the biosynthetic response of the source organisms to growth temperature. Multivariate temperature calibration can be expected to give more precise estimates of Integrated Production Temperatures (IPT) in the sedimentary record over a wider range of paleoenvironmental conditions, when derived using a calibration data set incorporating a similar range of natural variability in biosynthetic response.

Oxidation rate of thiosulfate and elemental sulfur in the Black Sea

Oxidation rate of 35S-thiosulfate under simulated natural conditions and abundance of thiosulfate-oxidizing bacteria in a redox zone of the Black Sea are lower during winter and spring than in summer, especially in halistatic regions. Oxidation of thiosulfate under natural conditions is performed chiefly by lithotropic thionic bacteria, whose activity is limited by low temperatures. Adding thiosulfate and readily available organic matter to water samples from the redox zone and raising temperature of water stimulated activity of heterotrophic thiosulfate-oxidizing bacteria. Oxidation of elemental sulfur tagged with 35S apparently invovled two stages: abiotic oxidation of thiosulfate and subsequent bacterial oxidation of thiosulfate to sulfate.

Composition of Fe-Mn micronodules, nodules and host bottom sediments from the Northeast Pacific Basin

Authigenic ferromanganese manifestations in bottom sediments from two horizons (0-10 and 240-250 cm) located in the low/high bioproductive transitional zone of the Pacific Ocean were studied. In addition two compositionally different types of micronodules, crusts and ferromanganese nodules were detected in the surface horizon (0-1 cm). Three size fractions (50-100, 100-250, and 250-500 µm) of manganese micronodules were investigated. In terms of surface morphology, color, and shape, the micronodules are divided into dull round (MN1) and angular lustrous (MN2) varieties with different mineral and chemical compositions. MN1 are enriched in Mn and depleted in Fe as compared with MN2. Mn/Fe ratio in MN1 varies from 13 to 14. Asbolane-buserite and birnessite are the major manganese minerals in them. MN2 is mainly composed of vernadite with Mn/Fe ratio from 4.3 to 4.8. Relative to MN1, fraction 50-100 µm of MN2 is enriched in Fe (2.6 times), W (1.8), Mo (3.2), Th (2.3), Ce (5.8), and REE (from 1.2 to 1.8). Relative to counterparts from MN1, separate fractions of MN2 are characterized by greater compositional difference. For example, increase in size of micronodules leads to decrease in contents of Fe (by 10 rel. %), Ce (2 times), W (2.1 times), Mo (2.2 times), and Co (1.5 times). At the same time one can see increase in contents of other elements: Th and Cu (2.1 times), Ni (1.9 times), and REE (from 1.2 to 1.6 times). Differences in chemical and mineral compositions of MN1 and MN2 fractions can be related to alternation of oxidative and suboxidative conditions in the sediments owing to input of labile organic matter, which acts as the major reducer, and allochthonous genesis of MN2.

Chemical composition of hydrothermal deposits and vulcanites from the Menez Gwen vent field, Mid-Atlantic Ridge

Surface hydrothermal deposits of the shallow-water Menez Gwen vent field located in the rift zone of the Mid-Atlantic Ridge are mostly composed of nonmetalliferous minerals in contrast to sulfide deposits of deep-water fields. Here sulfide minerals occur only in dispersed form. High-temperature sulfide deposits strongly enriched in copper and zinc occur only immediately below the surface of the bottom. This is related to subsurface boiling and phase separation of initial high-temperature hydrothermal ore-bearing solution that ascends from the interior to the floor surface.

(Table 1) Chemical composition of Middle Cenozoic magmatic rocks from the Schmidt Peninsula, North Sakhalin

Middle Cenozoic evolution of magmatism in the Schmidt Peninsula between 37 and 25 Ma began with eruptions of subalkaline and moderately alkaline andesite, latite, trachyandesite, and trachyrhyolite lavas and ended with subvolcanic intrusions of highly alkaline strongly undersaturated essexites. According to trace element data magmatism evolved from melting of a mantle source in the zone of ocean-continent plate convergence to small degree partial melting in the lithospheric mantle at the final stage. This succession is generally typical for Late Cenozoic continental-margin magmatism in the Southeast Russia. Similarity in the Middle and Late Cenozoic stages of magmatism is an evidence for their individual significance.

Description of two mass species of Pacific copepods in terms of two polymorphic loci

Population genetics of two species of mass copepods Undinula darwini and Calanus australis, with different range types, is investigated. Both species exhibit considerable genetic diversity, especially C. australis (observed heterozygoticity = 0.36), which inhabits a variable biotope in the zone of the Peru current. Samples of both species exhibited highly significant genetic heterogeneity as well as heterozygote deficiency compared with the situation expected from the Hardy-Weinberg law. Contribution of distance isolation to genetic differentiation of populations is estimated. Gene drift is discussed as a source of heterogeneity in populations of planktic copepods. Possible aspects of population genetic research on marine plank-tic crustaceans are discussed.