Paleomagnetic of DSDP Leg 90

Sediments recovered during Leg 90 (Sites 587-594, plus Site 586 cored during Leg 89) are, in general, extremely weakly magnetized carbonate oozes and chalks with NRM intensities seldom greater than 0.05 µG. The quality of the paleomagnetic records deteriorates with increasing depth caused by the combined effects of removal of primary magnetic oxides by sulfate reduction processes and the dispersal of magnetic grains during compaction. Magnetic reversal sequences are generally recognizable back to the Gilbert, 3.4 to 5.35 m.y., except at equatorial Site 586 where only the Brunhes/Matuyama boundary could be identified. Longer reversal records were obtained at Site 588 (to Chron 13, about 13 m.y.) and Site 594 (base of Chron 5, about 5.9 m.y.). Sediments are characterized by extremely high calcium carbonate contents (90-100%) with almost no biosiliceous components. Blebs and streaks of pyrite are common, and the presence of iron sulfides with poor magnetic stabilities is suspected, although not yet positively identified. Viscous components of magnetization are common, sometimes to the extent of dominating the primary remanence, and there is evidence to suggest that a magnetic remanence is imparted during core recovery. Siliceous carbonate oozes provide better paleomagnetic records than pure carbonate oozes.

Sulfur and iron speciations in bottom sediments from the southwest Caspian Sea

Speciations of sulfur (sulfide S, pyrite S, sulfate S) and of reactive iron (Fe3+, Fe2+, sulfide Fe) in bottom sediments have been studied in gravity cores and drill cores collected on the shelf of the southwest Caspian Sea. It has been shown that intensity of reduction processes, in particular sulfate reduction, as well as speciations of S and reactive Fe reflect the change of transgressive and regressive stages of the Caspian basin. Characteristic features for the investigated area are high sedimentation rate and high reactivity of organic matter entering bottom sediments.

Paleomagnetic analysis of ODP Site 133-820

Paleomagnetic analysis of sediment samples from Ocean Drilling Program (ODP) Leg 133, Site 820, 10 km from the outer edge of the Great Barrier Reef, is undertaken to investigate the mineral magnetic response to environmental (sea level) changes. Viscous remanent magnetization (VRM) of both multidomain and near-superparamagnetic origin is prevalent and largely obscures the primary remanence, except in isolated high-magnetization zones. The Brunhes/Matuyama boundary cannot be identified, but is expected to be below 120 mbsf. The only evidence that exists for a geomagnetic excursion occurs at about 33 mbsf (-135 k.y.). Only one-half the cores were oriented, and many suffered from internal rotation about the core axis, caused by coring and/or slicing. The decay of magnetic remanence below the surface layer (0-2 mbsf) is attributed to sulfate reduction processes. The magnetic susceptibility (K) record is central for describing and understanding the magnetic properties of the sediments, and their relationship to glacio-eustatic fluctuations in sea level. Three prominent magnetic susceptibility peaks, at about 7, 32, and 64 mbsf, are superimposed on a background of smaller susceptibility oscillations. Fluctuations in susceptibility and remanence in the ôbackgroundö zone are controlled predominantly by variations in the concentration, rather than the composition of ferrimagnetics, with carbonate dilution playing an important role (type-A properties). The sharp susceptibility maxima occur at the start of the marine transgressions following low stands in sea level (high d18O, glacial maxima), and are characterized by a stable single-domain remanence, with a significant contribution from ultra-fine, superparamagnetic grains (type-C properties). During the later marine transgression, the susceptibility gradually returns to low values and the remanence is carried by stable single-domain magnetite (type-B properties). The A, B, and C types of sediment have distinctive ARM/K ratios. Throughout most of the sequence a strong inverse correlation exists between magnetic susceptibility and both CaCO3 and d18O variations. However, in the sharp susceptibility peaks (early transgression), more complex phase relationships are apparent among these parameters. In particular, the K-d18O correlation switches to positive, then reverts to negative during the course of the late transgression, indicating that two distinct mechanisms are responsible for the K-d18O correlation. Lower in the sequence, where sea-level-controlled cycles of upward-coarsening sediments, we find that the initial, mud phase of each cycle has been enriched in high-coercivity magnetic material, which is indicative of more oxic conditions. The main magnetic characteristics of the sediments are thought to reflect sea-level-controlled variations in the sediment source regions and related run-off conditions. Some preliminary evidence is seen that biogenic magnetite may play a significant role in the magnetization of these sediments.

AMS 14C ages and isotopic compositions of samples from the Derugin Basin, Sea of Okhotsk

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (~1%) in the barite fabric imply the presence of H2S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative d13C values of these carbonates (>-43.5 per mill PDB) indicate methane as major carbon source; d18O values between 4.04 and 5.88 per mill PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with 14C-ages ranging from 20 680 to >49 080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO4**2- concentrations and a parallel increase of H2S with depth. Additionally, S and O isotope data of barite sulfate (d34S: 21.0-38.6 per mill CDT; d18O: 9.0-17.6 per mill SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with 'normal' seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49 000 yr.

Chemical composition of sediments from the Indian Ocean

Intensive reduction processes within bottom sediments from the Bay of Bengal lead to marked enrichment of the oxidized layer in iron and manganese. This is not observed in sediments from the Arabian Sea. Oxidized bottom sediments in central areas of the Indian Ocean show high iron concentrations, but fraction of reactive Fe in total Fe is lower. Manganese concentration increases steadily with distance from the shore to the pelagic region of the ocean, and fraction of reactive manganese also increases in the same direction. There is close correlation between total Mn and Mn(4+) in these sediments.

(Table 3) Carbon and oxygen isotopic data of carbonates from Core SLR 37-1, HYC 25-1 and an aragonite crust from station DR 35-1

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (1%) in the barite fabric imply the presence of H2S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative ?13C values of these carbonates (>?43.5? PDB) indicate methane as major carbon source; ?18O values between 4.04 and 5.88? PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with 14C-ages ranging from 20 680 to >49 080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO42- concentrations and a parallel increase of H2S with depth. Additionally, S and O isotope data of barite sulfate (?34S: 21.0-38.6? CDT; ?18O: 9.0-17.6? SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with 'normal' seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49 000 yr.

Particel size distribution and microstructures of sediments from ODP Leg 205 sites (Table 1)

Ocean Drilling Program Legs 170 and 205 offshore Costa Rica provide structural observations which support a new model for the geometry and deformation response to the seismic cycle of the frontal sedimentary prism and decollement. The model is based on drillcore, thin section, and electron microscope observations. The decollement damage zone is a few tens of meters in width, it develops mainly within the frontal prism. A clear cm-thick fault core is observed 1.6 km from the trench. The lower boundary of the fault core is coincident with the lithological boundary between the frontal prism and the hemipelagic and pelagic sediment of the Cocos plate. Breccia clast distributions in the upper portion of the decollement damage zone were studied through fractal analysis. This analysis shows that the fractal dimension changes with brecciated fragment size, implying that deformation was not accommodated by self-similar fracturing. A higher fractal dimensionality correlates with smaller particle size, which indicates that different or additional grain-size reduction processes operated during shearing. The co-existence of two distinct fracturing processes is also confirmed by microscopic analysis in which extension fracturing in the upper part of the damage zone farthest from the fault core is frequent, while both extension and shear fracturing occur approaching the fault core. The coexistence of extensional and shear fracturing seems to be best explained by fluid pressure variations in response to variations of the compressional regime during the seismic cycle. During the co-seismic event, sub-horizontal compression and fluid pressure increase, triggering shear fracturing and fluid expulsion. Fractures migrate upward with fluids, contributing to the asymmetric shape of the decollement, while slip propagates. In the inter-seismic interval the frontal prismrelaxes and fluid pressure drops. The frontal prismgoes into diffuse extension during the intervalwhen plate convergence is accommodated by creep along the ductile fault core. The fault core is typically a barrier to deformation, which is explained by its weak, but impermeable, nature. The localized development of a damage zone beneath the fault core is characterized by shear fracturing that appears as the result of local strengthening of the detachment.

Nitrogen isotopic composition and chemical composition of altered oceanic crust from ODP Legs 129 and 185

Knowledge of the subduction input flux of nitrogen (N) in altered oceanic crust (AOC) is critical in any attempt to mass-balance N across arc-trench systems on a global or individual-margin basis. We have employed sealed-tube, carrier-gas-based methods to examine the N concentrations and isotopic compositions of AOC. Analyses of 53 AOC samples recovered on DSDP/ODP legs from the North and South Pacific, the North Atlantic, and the Antarctic oceans (with larger numbers of samples from Site 801 outboard of the Mariana trench and Site 1149 outboard of the Izu trench), and 14 composites for the AOC sections at Site 801, give N concentrations of 1.3 to 18.2 ppm and d15N_air of -11.6? to +8.3?, indicating significant N enrichment probably during the early stages of hydrothermal alteration of the oceanic basalts. The N-d15N modeling for samples from Sites 801 and 1149 (n=39) shows that the secondary N may come from (1) the sedimentary N in the intercalated sediments and possibly overlying sediments via fluid-sediment/rock interaction, and (2) degassed mantle N2 in seawater via alteration-related abiotic reduction processes. For all Site 801 samples, weak correlation of N and K2O contents indicates that the siting of N in potassic alteration phases strongly depends on N availability and is possibly influenced by highly heterogeneous temperature and redox conditions during hydrothermal alteration. The upper 470-m AOC recovered by ODP Legs 129 and 185 delivers approximately 800 kg/km N annually into the Mariana margin. If the remaining less-altered oceanic crust (assuming 6.5 km, mostly dikes and gabbros) has MORB-like N of 1.5 ppm, the entire oceanic crust transfers 5100 kg/km N annually into that trench. This N input flux is twice as large as the annual N input of 2500 kg/km in seafloor sediments subducting into the same margin, demonstrating that the N input in oceanic crust, and its isotopic consequences, must be considered in any assessment of convergent margin N flux.

Interstitial water chemistry at DSDP Leg 79 Holes

Interstitial water analyses of samples collected at Sites 544-547 of DSDP Leg 79 are presented. In Site 547 chloride concentrations increase to almost 80% of the halite saturation values. Gypsum occurrences in the sediments immediately overlying the halite deposit can be explained in terms of migration of Ca**2+ and SO2**2- from the underlying evaporites. At shallower depths sulfate concentrations decrease rapidly as a result of sulfate reduction processes. The same processes lead to the removal of calcium in the form of calcium carbonate. At Site 547, the chloride concentration depth profile suggests a maximum of dissolved chloride which may be the result of advective flow from nearby (abput 6 km) evaporite salt diapirs.

Geochemistry and geomicrobiology profiles of ferruginous sediment, Lake Towuti, Indonesia

Lake Towuti is a tectonic basin, surrounded by ultramafic rocks. Lateritic soils form through weathering and deliver abundant iron (oxy)hydroxides but very little sulfate to the lake and its sediment. To characterize the sediment biogeochemistry, we collected cores at three sites with increasing water depth and decreasing bottom water oxygen concentrations. Microbial cell densities were highest at the shallow site - a feature we attribute to the availability of labile organic matter and the higher abundance of electron acceptors due to oxic bottom water conditions. At the two other sites, OM degradation and reduction processes below the oxycline led to partial electron acceptor depletion. Genetic information preserved in the sediment as extracellular DNA provides information on aerobic and anaerobic heterotrophs related to Actinobacteria, Nitrospirae, Chloroflexi and Thermoplasmatales. These taxa apparently played a significant role in the degradation of sinking organic matter. However, extracellular DNA concentrations rapidly decrease with core depth. Despite very low sulfate concentrations, sulfate-reducing bacteria were present and viable in sediments at all three sites, as confirmed by measurement of potential sulfate reduction rates. Microbial community fingerprinting supported the presence of taxa related to Deltaproteobacteria and Firmicutes with demonstrated capacity for iron and sulfate reduction. Concomitantly, sequences of Ruminococcaceae, Clostridiales and Methanomicrobiales indicated potential for fermentative hydrogen and methane production. Such first insights into ferruginous sediments show that microbial populations perform successive metabolisms related to sulfur, iron and methane. In theory, iron reduction could reoxidize reduced sulfur compounds and desorb OM from iron minerals to allow remineralization to methane. Overall, we found that biogeochemical processes in the sediments can be linked to redox differences in the bottom waters of the three sites, like oxidant concentrations and the supply of labile OM. At the scale of the lacustrine record, our geomicrobiological study should provide a means to link the extant subsurface biosphere to past environments.

Composition of free lipids in bottom sediments in the tropical West Pacific and South Atlantic

Contents of free lipids in the upper layers of slightly siliceous diatomaceous oozes from the South Atlantic and of calcareous foraminiferal oozes, of coral sediments and of red clays from the western tropical Pacific amount varies from 0.014 to 0.057% of dry sediment. Their content is inversely proportional to total content of organic matter. Relative content of low-polar compounds in total amount of lipids and content of hydrocarbons, fatty acids, and sterols in the composition of these compounds can serve as an index of degree of transformation of organic matter in sediment because these compounds are resistant to various degree to microbial and hydrolytic decomposition and, consequently, are selectively preserved under conditions of biodegradation of organic compounds during oxydation-reduction processes.

Solid phase phosphorus geochemistry in surface sediments of sediment cores GeoB3718-4, GeoB3702-2 and GeoB3707-4

In this study we investigate benthic phosphorus cycling in recent continental margin sediments at three sites off the Namibian coastal upwelling area. Examination of the sediments reveals that organic and biogenic phosphorus are the major P-containing phases preserved. High Corg/Porg ratios just at the sediment surface suggest that the preferential regeneration of phosphorus relative to that of organic carbon has either already occurred on the suspension load or that the organic matter deposited at these sites is already rather refractory. Release of phosphate in the course of benthic microbial organic matter degradation cannot be identified as the dominating process within the observed internal benthic phosphorus cycle. Dissolved phosphate and iron in the pore water are closely coupled, showing high concentrations below the oxygenated surface layer of the sediments and low concentrations at the sediment-water interface. The abundant presence of Fe(III)-bound phosphorus in the sediments document the co-precipitation of both constituents as P-containing iron (oxyhydr)oxides. However, highly dissolved phosphate concentrations in pore waters cannot be explained, neither by simple mass balance calculations nor by the application of an established computer model. Under the assumption of steady state conditions, phosphate release rates are too high as to be balanced with a solid phase reservoir. This discrepancy points to an apparent lack of solid phase phosphorus at sediment depth were suboxic conditions prevail. We assume that the known, active, fast and episodic particle mixing by burrowing macrobenthic organisms could repeatedly provide the microbially catalyzed processes of iron reduction with authigenic iron (oxyhydro)oxides from the oxic surface sediments. Accordingly, a multiple internal cycling of phosphate and iron would result before both elements are buried below the iron reduction zone.

Methane and microbiological processes in the Barents Sea

Biogeochemical cycle of methane in the Barents Sea was studied using isotope geochemistry to determine rates of microbial methane oxidation. It was established that microbiological processes (glucose consumption, 14CO2 assimilation, sulfate reduction, and slow methane oxidation) in oxidized surface and weakly reduced sediments are marked by only insignificant change in SO4 concentration and absence of notable increase of total alkalinity and N/NH4 downward sediment cores. Microbial methane productivity was 0.111x10**6 mol/day. Taking into account volume of the water column, microbial methane consumption therein can be as much as 1.8x10**6 mol/day.