Geochemistry and isotopes at DSDP Site 76-533

Concentrations and d34S and d13C values were determined on SO4, HCO3, CO2, and CH4 in interstitial water and gas samples from the uppermost 400 m of sediment on the Blake Outer Ridge. These measurements provide the basis for detailed interpretation of diagenetic processes associated with anaerobic respiration of electrons generated by organic- matter decomposition. The sediments are anaerobic at very shallow depths (<1 m) below the seafloor. Sulfate reduction is confined to the uppermost 15 m of sediment and results in a significant outflux of oxidized carbon from the sediments. At the base of the sulfate reduction zone, upward-diffusing CH4 is being oxidized, apparently in conjunction with SO4 reduction. CH4 generation by CO2 reduction is the most important metabolic process below the 15-m depth. CO2 removal is more rapid than CO2 input over the depth interval from 15 to 100 m, and results in a slight decrease in HCO3 concentration accompanied by a 40 per mil positive shift in d13C. The differences among coexisting CH4, CO2, and HCO3 are consistent with kinetic fractionation between CH4 and dissolved CO2, and equilibrium fractionation between CO2 and HCO3. At depths greater than 100 m, the rate of input of CO2 (d13C = -25 per mil) exceeds by 2 times the rate of removal of CO2 by conversion to CH4 (d13C of -60 to -65 per mil). This results in an increase of dissolved HCO3 concentration while maintaining d13C of HCO3 relatively constant at +10 per mil. Non-steady-state deposition has resulted in significantly higher organic carbon contents and unusually high (70 meq/l) pore-water alkalinities below 150 m. These high alkalinities are believed to be related more to spontaneous decarboxylation reactions than to biological processes. The general decrease in HCO3 concentration with constant d13C over the depth interval of 200 to 400 m probably reflects increased precipitation of authigenic carbonate. Input-output carbon isotope-mass balance calculations, and carbonate system equilibria in conjunction with observed CO2-CH4 ratios in the gas phase, independently suggest that CH4 concentrations on the order of 100 mmol/kg are present in the pore waters of Blake Outer Ridge sediments. This quantity of CH4 is believed to be insufficient to saturate pore waters and stabilize the CH4*6H2O gas hydrate. Results of these calculations are in conflict with the physical recovery of gas hydrate from 238 m, and with the indirect evidence (seismic reflectors, sediment frothing, slightly decreasing salinity and chlorinity with depth, and pressure core barrel observations) of gas-hydrate occurrence in these sediments. Resolution of this apparent conflict would be possible if CH4 generation were restricted to relatively thin (1-10 m) depth intervals, and did not occur uniformly at all depths throughout the sediment column, or if another methanogenic process (e.g., acetate fermentation) were a major contributor of gas.

Geochemistry of ODP Sites 128-798 and 128-799 sediments

Nineteen trace elements, including seven rare earth elements (REE's), and 10 major and minor elements in 76 sediment samples from Sites 798 (Oki Ridge) and 799 (Yamato Trough) were determined by means of instrumental neutron activation analysis and X-ray fluorescence spectrometry. Most REE patterns (chondrite-normalized) of the sediments from both sites were nearly identical to the patterns of terrigenous materials. The cerium anomaly (slightly positive) frequently appeared in REE patterns of the sediments (200-750 mbsf) from Site 799. Cerium may be selectively incorporated into the sediments with hydrogenous manganese precipitation. However, the degree of the anomaly was not well correlated with manganese content, suggesting that cerium may behave as a trivalent REE (like the other REE's) during diagenesis while manganese is transported in the sediment column accompanied by reduction to a lower oxidation state. The Th/Sc ratio of the sediments from Sites 798 and 799 tended to decrease with penetration depth. Such a depth profile may indicate a decrease in basic volcanism activities from the Pliocene (Site 798) and Miocene (Site 799). The La/Yb ratio and degree of europium anomaly also varied with depth, which may imply that two or more components with different REE patterns were supplied throughout sedimentation at sites in the Japan Sea.

Geochemistry of reduction haloes in ODP Holes 135-834A and 135-837A

The sediment column overlying basement in the Lau Basin consists of a sequence of volcaniclastic turbidites interbedded with hemipelagic clayey nannofossil mixed sediments, overlain in turn by a sequence of hemipelagic clayey nannofossil oozes containing sporadic calcareous turbidites. The clayey nannofossil oozes and mixed sediments are pervasively stained by hydrothermally derived iron and manganese oxyhydroxides. Sharply defined, lighter colored bands occur in the hemipelagic sediments, immediately beneath some (but by no means all) volcaniclastic and calcareous turbidites. These are identified as reduction haloes, of a type previously identified in quite different turbidite/pelagic sequences. The haloes are attributed to the burial of labile surficial Corg by turbidites, followed by the remineralization of this Corg with Mn and Fe oxyhydroxides as electron acceptors. The resultant characteristic Mn and Fe concentration/depth profiles are described, and a model is proposed for their development. The color alteration of the halo is ascribed to the removal of Mn oxyhydroxides, because, although the Fe content fluctuates through the haloes, this does not appear to affect their color. Other elements (Co, Cu, and Ni) are also at low concentration levels in the haloes like Mn, consistent with remobilization and migration out of the halo section, although the profile shapes are not identical with those of Mn. The behavior of V is distinctive in that it appears to have migrated into the haloes to be enriched there. Haloes are unlikely to form if turbidite emplacement is erosive and removes the near-surface layer, which generally is the most fluid part of the sediment and contains the highest levels of reactive Corg to drive the reduction process. Conversely, the presence of a halo implies that emplacement of the overlying turbidite did not significantly erode the pre-existing sediment/water interface.

Geochemical and biogeochemical parameters of bottom sediments from the area of the Spitsbergen (Svalbard) Archipelago

Quantitative characteristics for rates of diagenetic processes in the upper (0-30 cm) layer of sedimentary deposits in the area of the Spitsbergen (Svalbard) Archipelago (78°-80°N) were obtained by lithologo-geochemical, radioisotope (35S, 14C), and stable isotope (d34S, d13C) studies. It was proved that rates of diagenetic processes in polar deposits at 123-395 m depth affected by the East Spitsbergen ''warm'' current are mostly determined by bioproductivity and are commensurate with rates of processes in shelf deposits of temperate latitudes. High contents of migratory methane (up to 263 ml/dm**3) and isotopically-light organic carbon (Corg, d13C = -30 per mil PDB) were found in the 1 m layer of shelf deposits (at 123 m sea depth) with low bacterial in situ production of methane. It was shown that methane is not utilized in the deposits by the methanotrophic bacterial community and it may be supplied to the water mass and, probably, to the atmosphere.

Chemical composition of bottom sediments at DSDP Sites 91-595 and 91-596 and ODP Sites 114-701 and 129-801

Subducted sediments play an important role in arc magmatism and crust-mantle recycling. Models of continental growth, continental composition, convergent margin magmatism and mantle heterogeneity all require a better understanding of the mass and chemical fluxes associated with subducting sediments. We have evaluated subducting sediments on a global basis in order to better define their chemical systematics and to determine both regional and global average compositions. We then use these compositions to assess the importance of sediments to arc volcanism and crust-mantle recycling, and to re-evaluate the chemical composition of the continental crust. The large variations in the chemical composition of marine sediments are for the most part linked to the main lithological constituents. The alkali elements (K, Rb and Cs) and high field strength elements (Ti, Nb, Hf, Zr) are closely linked to the detrital phase in marine sediments; Th is largely detrital but may be enriched in the hydrogenous Fe-Mn component of sediments; REE patterns are largely continental, but abundances are closely linked to fish debris phosphate; U is mostly detrital, but also dependent on the supply and burial rate of organic matter; Ba is linked to both biogenic barite and hydrothermal components; Sr is linked to carbonate phases. Thus, the important geochemical tracers follow the lithology of the sediments. Sediment lithologies are controlled in turn by a small number of factors: proximity of detrital sources (volcanic and continental); biological productivity and preservation of carbonate and opal; and sedimentation rate. Because of the link with lithology and the wealth of lithological data routinely collected for ODP and DSDP drill cores, bulk geochemical averages can be calculated to better than 30% for most elements from fewer than ten chemical analyses for a typical drill core (100-1000 m). Combining the geochemical systematics with convergence rate and other parameters permits calculation of regional compositional fluxes for subducting sediment. These regional fluxes can be compared to the compositions of arc volcanics to asses the importance of sediment subduction to arc volcanism. For the 70% of the trenches worldwide where estimates can be made, the regional fluxes also provide the basis for a global subducting sediment (GLOSS) composition and flux. GLOSS is dominated by terrigenous material (76 wt% terrigenous, 7 wt% calcium carbonate, 10 wt% opal, 7 wt% mineral-bound H2O+), and therefore similar to upper continental crust (UCC) in composition. Exceptions include enrichment in Ba, Mn and the middle and heavy REE, and depletions in detrital elements diluted by biogenic material (alkalis, Th, Zr, Hf). Sr and Pb are identical in GLOSS and UCC as a result of a balance between dilution and enrichment by marine phases. GLOSS and the systematics of marine sediments provide an independent approach to the composition of the upper continental crust for detrital elements. Significant discrepancies of up to a factor of two exist between the marine sediment data and current upper crustal estimates for Cs, Nb, Ta and Ti. Suggested revisions to UCC include Cs (7.3 ppm), Nb (13.7 ppm), Ta (0.96 ppm) and TiO2 (0.76 wt%). These revisions affect recent bulk continental crust estimates for La/Nb and U/Nb, and lead to an even greater contrast between the continents and mantle for these important trace element ratios. GLOSS and the regional sediment data also provide new insights into the mantle sources of oceanic basalts. The classical geochemical distinction between 'pelagic' and 'terrigenous' sediment sources is not valid and needs to be replaced by a more comprehensive understanding of the compositional variations in complete sedimentary columns. In addition, isotopic arguments based on surface sediments alone can lead to erroneous conclusions. Specifically, the Nd/Hf ratio of GLOSS relaxes considerably the severe constraints on the amount of sediment recycling into the mantle based on earlier estimates from surface sediment compositions.

Carbonate, organic carbon and nitrogen, bitumen and rock-eval pyrolysis at DSDP Leg 79 Holes

The lipids and kerogens of 15 sediment samples from Site 547 (ranging from Pleistocene to Early Jurassic/Triassic) and 4 from Site 545 (Cretaceous) have been analyzed. A strong terrestrial contribution of organic matter was found, and significant autochthonous inputs were also present, especially at Site 545. Both strongly reduced and highly oxidized sediments have been found in the Cenozoic and Jurassic samples of Site 547. On the contrary, all the Cretaceous sections of Sites 547 and 545 are anoxic. Sediments from anoxic paleoenvironments are immature and have a high content of sterenes, diasterenes, steradienes, hopenes, and ßß hopanes. Samples from oxic paleoenvironments are mainly mature and their content of hopenes and steriod structures is below the detection level. Nevertheless, their hopane distributions have the immature ßß homologs as the predominant molecular markers. For Site 545 the most abundant molecular markers are ring A monoaromatic steranes, and their presence is attributed to microbial and chemical transformations during early diagenesis.

Bulk and clay mineralogy of ODP Leg 110 holes

The mineralogy of both bulk- and clay-sized fractions of samples from Sites 671, 672, and 674 of ODP Leg 110 was determined by X-ray diffraction. The major minerals include quartz, calcite, plagioclase feldspar, and the clay minerals smectite, illite, and kaolinite. The smectite is a dioctahedral montmorillonite and is derived primarily from degradation of volcanic ash. Percentage of smectite varies with sediment age; Miocene and Eocene sediments are the most smectite-rich. High smectite content tends to correlate with elevated porosity, presumably because of the ability of smectite clays to absorb significant amounts of interlayer water. Because of a change in physical properties, the decollement zone at Site 671 formed in sediments immediately subjacent to a section of smectite-rich, high-porosity, Miocene-age sediments. Sediments above the decollement at Site 671, as well as all sediments analyzed from Sites 672 and 674, contain nearly pure smectite characteristic of the alteration of volcanic ash. Within the decollement zone and underthrust sequence, however, the smectite contains up to 65% illite interlayers. Although the illite/smectite could be interpreted as detrital clay derived from South America, its absence in the sediments stratigraphically equivalent to the decollement and underthrust sequences at Sites 672 and 674 favors the interpretation that it originated by diagenetic alteration of pre-existing smectite similar to that in the overlying sediments. A significant percentage of the freshening of the pore waters observed in these zones could be due to the water released during smectite dehydration.

Organic carbon, age, lithology, and CPI-alkenes at DSDP Sites 57-440 and 56-436

"Bound" and "free" solvent-extractable lipids have been examined from Sections 440A-7-6, 440B-3-5, 440B-8-4, 440B-68-2, and 436-11-4. The compound classes studied include aliphatic and aromatic hydrocarbons, ketones, alcohols, and carboxylic acids. Carotenoids and humic acids have also been examined. The quantitative results are considered in terms of input indicators, diagenesis parameters, and structural classes. A difference in input is deduced across the Japan Trench, with a higher proportion of autochthonous components on the western inner trench slope compared with the more easterly, outer trench, wall and greater input in the early Pleistocene than in the Miocene. A variety of diagenetic transformations is observed at Site 440 as sample depth increases. Results are compared with those of samples from Atlantic Cretaceous sediments and from the Walvis Bay high productivity area.

Chemostratigraphy (CaCO3, TOC, d13Corg) of Sinemurian black shales

The Shales-with-'Beef' and Black Ven Marls of the Charmouth Mudstone Formation (Sinemurian) exposed on the Dorset Coast in southern England (Wessex Basin) show stratigraphic variation in carbonate, organic carbon and organic-carbon isotopes. Little environmental significance is attached to the variation of carbonate except in the case of the tabular and nodular limestones interrupting the sequence that probably record stratigraphic condensation and/or sedimentary stillstands that, in an extreme case, were accompanied by sea-floor erosion to produce the bored and encrusted 'Coinstone'. Relatively high total organiccarbon (TOC) contents are present in the laminated mudstones of the lower turneri Zone (upper brooki and lower birch Subzones) and the obtusum Zone (obtusum and stellare Subzones). Basin stratification related to fresh-water influx was the most likely aid to deoxygenation and enhanced preservation of organic matter. The organic-carbon isotope curve (d13Corg), which shows positive excursions in the upper turneri Zone (upper birchi Subzone) and highest obtusum - raricostatum Zones (highest stellare Subzone, densinodulum and lower raricostatoides Subzones), does not correlate with the TOC stratigraphy and was clearly not controlled by local patterns of organic-matter burial. Long-term (hundreds-of-thousands of years) variations in the carbon-isotope (d13Corg) curve are interpreted as reflecting changing seawater isotopic composition and, in the case of the stratigraphically higher interval, may be related to marine organic-carbon burial on the margins of the proto-Atlantic, as exemplified by the Lusitanian Basin in Portugal. Correlation of the carbon-isotope profile with putative sea-level curves is problematic in detail, although significant local transgressive pulses in the turneri and late raricostatum Zones are approximately coincident with positive d13Corg excursions.

Platinum-group element abundances in background samples and the K-T boundary interval from DSDP Hole 91-596 (Table 2)

New data on Ru/Ir abundance ratios are presented for nonmarine (Hell Creek, Montana; Frenchman River, Saskatchewan) and marine Cretaceous-Tertiary boundary sites (Brazos River, Texas; Beloc, Haiti; DSDP 577 and DSDP 596). The Ru/Ir ratio varies from 0.5 to 1 within 4000 km of Chicxulub and increases to 2-3 at paleodistances (65 Ma) of up to 12,000 km from the impact site. For CI chondrites, Ru/Ir = 1.5. A ballistic model of ejecta cloud cooling and expansion, which employs the available vapor-pressure versus temperature data for Ru and It, predicts qualitatively similar global variation in the Ru/Ir ratio but by only a factor of 1.5. We infer that several other factors, such as remobilization of PGE during diagenesis, preferential oxidation of Ru, condensation kinetics and atmospheric chemical and circulation processes, may account for the observed larger Ru/Ir variation.

Geochemistry and stable carbon isotope composition of kerogen of DSDP Site 124-767

Celebes Basin sediments from Ocean Drilling Program Site 767 (Leg 124) containing both marine and terrestrial organic matter have been investigated through palynofacies and geochemical analyses. The main degradation processes affecting or having affected organic matter are recorded in the sedimentary column as shown by ammonium, phosphate and sulfate pore-water profiles, and by petrographic and geochemical analyses of sediments. In the upper part of the sedimentary section (down to 200 mbsf), the decrease of the ratio of total organic carbon to sulfur (TOC/S) with depth, generally related to the sulfate reduction process, is accompanied by an increase of framboidal pyrite content in the marine organic matter, and by an increasing amount of amorphous marine organic matter relative to the total organic matter. However, as the terrestrial organic input also varies with depth, dilution effects are superimposed on diagenesis. This continental supply affects the TOC/S ratio by increasing total organic carbon and decreasing the ability of the bulk organic matter to be metabolized through sulfate reduction. A positive relationship between the TOC/P ratio and the amount of degraded organic matter of marine origin clearly displays the effect of an organic source on the composition of the sediment. Each lithostratigraphic unit possesses its own characteristics in terms of composition and preservation of organic matter. The effects of diagenesis can only be appreciated within a single lithostratigraphic unit and mainly affect the less-resistant marine organic matter.

Osmium isotope composition of ODP Hole 121-758A

This study presents osmium (Os) isotope and elemental data for cleaned planktic foraminifera, authigenic Fe-Mn oxyhydroxides and pelagic carbonate host sediments from ODP site 758 in the southernmost reaches of the Bay of Bengal. The Os in the bulk sediments appears to be dominantly hydrogeneous (sourced by carbonate and Fe-Mn oxyhydroxide), but variations in this particular core are controlled by the presence of volcanic ash. Fe-Mn oxyhydroxide leachates (of the bulk sediments) from Holocene samples also yield an Os isotope composition close to that of seawater, but the record diverges from that of foraminifera at a depth corresponding to the oxic/post-oxic boundary, suggesting diagenetic mobilization of Os at depths below this. Holocene planktic foraminifera, cleaned using oxidative-reductive techniques, also give Os isotope compositions indistinguishable from modern seawater, but the record obtained for the past 150 kyr shows strong covaraitions of 187Os/188Os with both the local and global oxygen isotope record, with less radiogenic Os isotope compositions during glacial intervals. These results indicate that foraminifera provide a robust record of seawater Os isotope compositions, and comparison of the data obtained here with records from the other major oceans demonstrate global changes in 187Os/188Os over this time interval, while the covariation with oxygen isotopes suggest a process controlling the Os isotope composition that is in phase with global climate cycles. Global excursions to relatively unradiogenic 187Os/188Os during glacial intervals are consistent with decreased input of radiogenic continental material, reflecting cooler temperatures and reduced continental runoff. Modelling indicates that the shift to unradiogenic values during glacial intervals could be caused by an ~30% decrease in the global river flux, with an ~5% change in river composition. If the residence time of Os in the oceans is ~5 ka then the post-glacial recovery to present-day seawater values is consistent with a corresponding increase in the river flux of around 30%. However, if the residence time of Os is closer to 40 ka, as is suggested by the global river flux, then this demands either significant changes in both the riverine Os flux and composition of around 40% and 30%, respectively, that closely follow the oxygen isotope record, or else a short-lived post-glacial pulse of weathering some 75% greater than the steady-state flux. In either case, these results clearly indicate that climatic changes affect both the flux and composition of weathered material delivered to the oceans on glacial-interglacial timescales.