(Table 1) Sulfur isotopes and sulfur content at DSDP Leg 64 Holes

Hydrothermal pyrite samples from Holes 477, 477A, and 478 have sulfur isotope values ranging from about 10 to 11 per mil. Samples with negative sulfur isotope values generally have low sulfide sulfur contents and reflect mixed bacterial and hydrothermal sulfur sources. At higher sulfur contents, the hydrothermal component predominates, producing positive isotope values. Hydrothermal sulfide derives from reduction of seawater sulfate and may contain a significant basaltic component. Hydrothermal anhydrite is restricted to a narrow zone beneath a dolerite sill at Site 477 and, because of partial sulfate reduction in the circulating waters, has isotopic values (23.5-25 per mil), heavier than seawater.

Pore water isotopic ratios of CO2 and SO4, and sediment CH4 content of ODP Leg 164 sites

A unique set of geochemical pore-water data, characterizing the sulfate reduction and uppermost methanogenic zones, has been collected at the Blake Ridge (offshore southeastern North America) from Ocean Drilling Program (ODP) Leg 164 cores and piston cores. The d13C values of dissolved CO2 (sum CO2) are as 13C-depleted as -37.7 per mil PDB (Site 995) at the sulfate-methane interface, reflecting a substantial contribution of isotopically light carbon from methane. Although the geochemical system is complex and difficult to fully quantify, we use two methods to constrain and illustrate the intensity of anaerobic methane oxidation in Blake Ridge sediments. An estimate using a two-component mixing model suggests that ~24% of the carbon residing in the sum CO2 pool is derived from biogenic methane. Independent diagenetic modeling of a methane concentration profile (Site 995) indicates that peak methane oxidation rates approach 0.005 µmol/cm**3/yr, and that anaerobic methane oxidation is responsible for consuming ~35% of the total sulfate flux into the sediments. Thus, anaerobic methane oxidation is a significant biogeochemical sink for sulfate, and must affect interstitial sulfate concentrations and sulfate gradients. Such high proportions of sulfate depletion because of anaerobic methane oxidation are largely undocumented in continental rise sediments with overlying oxic bottom waters. We infer that the additional amount of sulfate depleted through anaerobic methane oxidation, fueled by methane flux from below, causes steeper sulfate gradients above methane-rich sediments. Similar pore water chemistries should occur at other methane-rich, continental-rise settings associated with gas hydrates.

Hydrocarbon gar in sediments of the Costa Rica ubduction zone

At the active continental margin off Costa Rica substantial amounts of hydrocarbon gases are encountered in sediments. The molecular composition (C1-C3) of free hydrocarbon gas as well as the isotopic composition (d13C of methane and ethane and D of methane) was analysed on core samples (ranging between 50 and 380 m depth) collected at sites 1040-1043 which was drilled during ODP Leg 170. In addition, the molecular composition of the C1-C3 hydrocarbons and the d13C composition of C1 and C2 hydrocarbons was determined on adsorbed gas from selected depth intervals at Site 1041 (50-380 mbsf). The molecular composition, and stable carbon and hydrogen isotope signature of low molecular weight hydrocarbons from core sediments and gas pockets indicate that most of the gas was generated by microbial CO2-reduction. Beside d13C values of about -80 per mil for methane (which is typical for microbially- generated methane) extremely light d13C values of -55 per mil were measured for ethane. The carbon isotope composition of methane and ethane, as well as the C1/(C2+C3) ratio display distinct trends with increasing depth. Gas mixing calculations indicate that the percentage of thermally-generated ethane increases from 10% at about 75 mbsf to almost 80% at 380 mbsf. The fraction of thermogenic methane in this depth interval is calculated to range from 0.03 to 1.8% of the total methane. The small contribution of thermogenic methane would increase the d13C value by <1 per mil. Therefore, the increase of d13C of methane (by about 12 per mil) with depth cannot be explained by gas mixing alone. Instead, the observed d13C trend is caused by successive isotope depletion of the methane precursor within the sedimentary organic matter due to progressing microbial gas generation.

Stable isotope ratios and geochemical composition of authigenic carbonates from ODP Sites 186-1150 and 186-1151

Several carbonaceous layers or fragments were recovered from sediments of Sites 1150 and 1151 on the deep-sea terrace of the Japan Trench during Leg 186. The X-ray diffraction analysis (XRD) data indicate that these are predominantly dolomitic. In this study, carbon and oxygen isotopes of these carbonates recovered at Sites 1150 and 1151 are presented. The oxygen isotope ratios of the dolomites analyzed range from +0.4 per mil to +4.1 per mil vs. Peedee formation belemnite (PDB) and those of calcites from +0.6 per mil to +2.8 per mil PDB. The isotopic composition of carbon varies from -7.0 per mil to +12.3 per mil PDB in dolomite and from -13.4 per mil to -24.1 per mil PDB in calcite. The wide range of carbon isotopic compositions indicates that the carbonate samples were formed by the decomposition of organic matter through reactions such as oxidation, sulfate reduction, and methane formation during diagenesis.

Sedimentology and geochemistry of the sand fraction in surface sediments off West Africa

Surface sediments from 5 profiles between 30 and 3000 m water depth off W Africa (12-19° N) have been studied for their sand fraction composition and their total calcium carbonate and organic matter contents to evaluate the effect of climatic and hydrographic factors on actual sedimentation. On the shelf and upper slope (< 500 m), currents prevent the deposition of significant amounts of fine-grained material. The sediments forming here are characterized by high sand contents (> 60 %; in most samples > 89 %), low organic carbon contents (in most samples < 0.8 %), high median diameters of the sand fraction (120-500 µm), and by a predominance of quartz and biogenic relict shells (most abundant: molluscs and bryozoans) in the sand fraction. Median diameters of total sand fraction and of major biogenic sand fraction components (biogenic relict material, benthonic molluscs, benthonic and planktonic foraminifers) co-vary to some extent and show maximum values in 100-300 m water depth, reflectingthe sorting effect of currents (perhaps the northward flowing undercurrent). In this water depth, biogenic relict material is considerably enriched relative to wuartz, the second dominating sand fraction component on the shelf and upper slope, resulting in distinct calcium carbonate maxima of the bulk sediments. The influence of the undercurrent is also reflected in a northward transport of fine grained river load and perhaps in the distribution of the red stained, coarse silt and sand-size clay aggregates, which show maxima in 300-500 m water depth. They probably originate from tropical soils. Abundant coarse red-stained quartz on the shelf off Cape Roxo (12-130° N) suggests a southward extension of last glacial dune fields to this latitude. Below about 500 m water depth, current influence becomes negligible - as indicated by a strong decrease in sand content, a concomitant increase in sedimentary organic carbon contents (up to 2.5-3.5 %), and the occurence of high mica/quartz ratios in the sand fraction. Downslope transport, presumably due to the bioturbation mechanism, is indicated by the presence of coarse shelf-borne particles (glauconite, relict shells) down to about 1000 m water depth. The fine/coarse ratio (clay + silt/sand) of the sediments from water deoth > 500 m never exceed a value of 11 in northern latitudes (19° - 26° N), but shows distinct maxima, ranging from 50 to 120, at latitudes 18°, 17° 15°30', and 14° N in about 2000 m water depth. This distribution is attributed to the deposition of fine-grained river load at the continental slope between 18° and 14° N, brought into the sea by the Senegal and souther rivers and transported northward ny the undercurrent. Strong calcium carbonate dissolution is indicated by the complete disappearance of pteropodes (aragonite) and high fragmentation of the planktoic foraminifers (calcite) in sediments from water depth > 300-600 m. Fragmentation ratios of planktonic foraminifers were found to depend on the organic carbon/carbonate ratios of the sediment suggesting that calcite dissolution at the sea bottom may also be significant in shelf and continental slope water depths if the organic matter/carbonate ratio of the surface sediment is high and the test remain long enough within the oxidizing layer on the top of the sulfate reduction zone. The fact that in the region under study intensity and anual duration of upwelling decrease from north to south is neither reflected in the composition on the sand fraction (i.e. radiolarian and fish debris contents, radiolarian/planktonic foraminiferal ratios, benthos/plankton ratios of foraminifers), nor in the sedimentary organic carbon distribution. On the contrary, these parameters even show in comparable water depths a tendency for highest values in the south, partly because primary production rates remain high in the whole region, particularly on the shelf, due to the nutrient input by rivers in the south. In addition, several hydrographic, sedimentological and climatic factors severely affect their distribution - for example currents, dissolution, grain size composition, deposition of river load, and bulk sedimentation rats.

Ikaite of sediment cores from the Zaire deep-sea fan

Most concentration profiles of sulfate in continental margin sediments show constant or continuously increasing gradients from the benthic boundary layer down to the deep sulfate reduction zone. However, a very marked change in this gradient has been observed several meters below the surface at many locations, which has been attributed to anoxic sulfide oxidation or to non-local transport mechanisms of pore waters. The subject of this study is to investigate whether this feature could be better explained by non-steady state conditions in the pore-water system. To this end, data are presented from two gravity cores recovered from the Zaire deep-sea fan. The sediments at this location can be subdivided into two sections. The upper layer, about 10 m thick, consists of stratified pelagic deposits representing a period of continuous sedimentation over the last 190 kyr. It is underlain by a turbidite sequence measuring several meters in thickness, which contains large crystals of authigenic calcium carbonate (ikaite: CaCO3·6H2O). Ikaite delta13C values are indicative of a methane carbon contribution to the CO2 pool. Radiocarbon ages of these minerals, as well as of the adjacent bulk sediments, provide strong evidence that the pelagic sediments have overthrust the lower section as a coherent block. Therefore, the emplacement of a relatively undisturbed sediment package is postulated. Pore-water profiles show the depth of the sulfate-methane transition zone within the turbiditic sediments. By the adaptation of a simple transport-reaction model, it is shown that the change in the geochemical environmental conditions, resulting from this slide emplacement, and the development towards a new steady state are fully sufficient to explain all features related to the pore-water profiles, particularly, [SO4]2- and dissolved inorganic carbon (DIC). The model shows that the downslope transport took place about 300 yr ago.

TOC, carbonate, opal composition and trace element concentration from ODP Holes 175-1082A and 175-1084A

Distinctive light-dark color cycles in sediment beneath the Benguela Current Upwelling System indicate repetitive alternations in sediment delivery and deposition. Geochemical proxies for paleoproductivity and for depositional conditions were employed to investigate the paleoceanographic processes involved in creating these cycles in three mid-Pleistocene intervals from ODP Sites 1082 and 1084. Concentrations of total organic carbon (TOC) vary between 3.5 and 17.1%. Concentrations of CaCO3 vary inversely to TOC and Al, which suggests that both carbonate dissolution and terrigenous dilution contribute to the light-dark cycles. Opal concentrations are independent of both TOC and CaCO3, therefore eliminating diatom production and lateral transport of shelf material as causes of the light-dark cycles. d13Corg and d15Ntot values do not vary across light-dark sediment intervals, implying that the extent of relative nutrient utilization did not change. The stable d15Ntot values represent a balanced change in nitrate supply and export production and therefore indicate that productivity was elevated during deposition of the TOC-rich layers. Parallel changes in concentrations of indicator trace elements and TOC imply that changes in organic matter delivery influenced geochemical processes on the seafloor by controlling consumption of pore water oxygen. Cu, Ni, and Zn are enriched in the darker sediment as a consequence of greater organic matter delivery. Redox-sensitive metals vary due to loss (Mn and Ba) or enrichment (Mo) under reducing conditions created by TOC oxidation. Organic matter delivery impacts subsequent geochemical changes such as carbonate dissolution, sulfate reduction and the concentration of metals. Thus, export production is considered ultimately responsible for the generation of the color cycles.

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.

Calcium isotope ratios of porewaters of ODP Leg 204 holes

The calcium isotopic composition of porewaters and authigenic carbonates in the anoxic sediments of a convergent continental margin drilled during Ocean Drilling Program (ODP) provides first insight into the different processes that control Ca geochemistry in clastic marine, organic-rich sedimentary environments. In 4 sites drilled during Leg 204 at Hydrate Ridge (Cascadia Margin, offshore Oregon/USA), sulfate is consumed during anaerobic oxidation of methane and of organic matter via sulfate reduction within the upper meters of the sedimentary section. These reactions promote the precipitation of authigenic carbonates through the generation of bicarbonate, which is reflected in a pronounced decrease in calcium concentration. Although Ca isotope fractionation is observed during carbonate precipitation, Ca concentration in the pore fluids from ODP Leg 204 is decoupled from Ca isotopy, which seems to be mainly controlled by the release of light Ca isotopes that completely overprint the carbonate formation effect. Different processes, such as the release of organically bound Ca, ion exchange and ion pair formation may be responsible for the released light Ca. Deeper within the sedimentary section, additional processes such as ash alteration influence the Ca isotopic composition of the porewater. Two sites, drilled into the deeper core of the accretionary prism, reveal the nature of fluids which have reacted with the oceanic basement. These deep fluids are characterized by relatively high Ca concentrations and low d44/40Ca ratios.

Chemistry of interstitial waters of ODP Site 166-718

Preliminary data are presented on dissolved heavy metals in interstitial water samples collected at Site 718 of Ocean Drilling Program Leg 118. The heavy metals at this site are divided into three groups: Group I (B, K, Mn, Ni, Pb, total Si, total P, V) behaves like Mg, which decrease with depth; Group II (Ba, Cu, Sr, Ti) behaves like Ca, which increases with depth; and Group 111 (Cd, Co, Cr, Fe, Na, Mo, Zn) contains metals that are independent of depth. Mg decreases with depth from 50 mM at the seafloor to 21 mM at 900 mbsf. Mn in the sulfate reduction zone (1.0 to 2.8 ppm) is more highly concentrated than in the methane fermentation zone (0.23 to 0.50 ppm), except for Section 116-718-1H-1. A similar behavior is also observed for V and Pb. Ni, B, and K decrease non-uniformly with depth. Ca and Sr increase with depth at the same rates, indicating the dissolution of inorganic calcium carbonate by anaerobic oxidation of organic matter (Sayles, 1981, doi:10.1016/0016-7037(81)90132-0). The distribution of Ba with depth is very similar to those of Ca and Sr. Cu and Ti profiles trend to increase non-uniformly with depth. Fe is constant with depth. The sharp decrease in total silicate concentration at the seafloor probably indicates a decrease in the decomposition of siliceous biological matter (e.g., diatoms) and production of opal. The constant levels of Group 111, except for Na and Fe, may reveal equal sources of supply from surface seawater and the Himalayas over time.

Sulfur speciation in bottom sediments from deep-sea basins of the Atlantic Ocean

Distribution of reduced sulfur forms in vertical sediment sections in deep-sea basins of the Atlantic Ocean is under study. Presence of weak sulfate reduction process resulted from low concentrations of reactive organic matter and differing by characteristic features of the initial stage of development. Interpretation of results is given on the base of consideration of dynamic redox equilibrium in the system: reduced sulfur - dissolved oxygen.

Composition of pore water and diagenetic carbonates of ODP Site 123-765

Degradation of organic matter in slightly organic-rich (1 wt% organic carbon) Neogene calcareous turbidites of the Argo Basin at Site 765 by sulfate reduction results in pore-water phosphate, ammonium, manganese, and carbonate alkalinity maxima. Pore-water calcium and magnesium decrease in the uppermost 100 meters below seafloor (mbsf) in response to the precipitation of calcian dolomite with an average composition of Ca1.15Mg0.83Fe0.02(CO3)2. Clear, euhedral dolomite rhombs range from <1 to 40 µm in diameter and occur in trace to minor amounts (<1-2 wt%) in Pleistocene to Pliocene sediment (62-210 mbsf) The abundance of dolomite increases markedly (2-10 wt%) in Miocene sediment (210-440 mbsf). The dolomite is associated with diagenetic sepiolite and palygorskite, as well as redeposited biogenic low-Mg calcite and aragonitic benthic foraminifers. Currently, dolomite is precipitating at depth within the pore spaces of the sediment, largely as a result of aragonite dissolution. The rate of aragonite dissolution, calculated from the pore-water strontium profile, is sufficient to explain the amount of dolomite observed at Site 765. A foraminiferal aragonite precursor is further supported by the carbon and oxygen isotopic compositions of the dolomite, which are fairly close to the range of isotopic compositions observed for Miocene benthic foraminifers. Dolomite precipitation is promoted by the degradation of organic matter by sulfate-reducing bacteria because the lower pore-water sulfate concentration reduces the effect of sulfate inhibition on the dolomite reaction and because the higher carbonate alkalinity increases the degree of saturation of the pore waters with dolomite. Organic matter degradation also results in the precipitation of pyrite and trace amounts of apatite (francolite), and the release of iron and manganese to the pore water by reduction of Fe and Mn oxides. Spherical, silt-sized aggregates of microcrystalline calcian rhodochrosite occur in trace to minor amounts in Lower Cretaceous sediment from 740 to 900 mbsf at Site 765. A negative carbon isotopic composition suggests that the rhodochrosite formed early in the sulfate reduction zone, but a depleted oxygen isotopic composition suggests that the rhodochrosite may have recrystallized at deeper burial depths.

Niche differentiation among mat-forming, sulfide-oxidizing bacteria in chemosynthetic ecosystems of the Nile Deep Sea Fan (Eastern Mediterranean Sea)

Sulfidic muds of cold seeps on the Nile Deep Sea Fan are populated by different types of mat-forming sulfide-oxidizing bacteria. The predominant sulfide oxidizers of three different mats were identified by microscopic and phylogenetic analyses as (i) Arcobacter species producing cotton-ball-like sulfur precipitates, (ii) large filamentous sulfur bacteria including Beggiatoa species, or (iii) single, spherical cells resembling Thiomargarita species. High resolution in situ microprofiles revealed different geochemical settings selecting for different mat types. Arcobacter mats occurred where oxygen and sulfide overlapped at the bottom water interface. Filamentous sulfide oxidizers were associated with non-overlapping, steep gradients of oxygen and sulfide. A dense population of Thiomargarita was favored by temporarily changing supplies of oxygen and sulfide. These results indicate that the decisive factors in selecting for different mat-forming bacteria within one deep-sea province are spatial or temporal variations in energy supply. Furthermore, the occurrence of Arcobacter spp.-related 16S rRNA genes in the sediments below all three types of mats, as well as on top of brine lakes of the Nile Deep Sea Fan, indicates that this group of sulfide oxidizers can switch between different life modes depending on the geobiochemical habitat setting.

Organic geochemistry of interstitial waters at DSDP Holes 64-474 and 64-479

Studies of the nature and amount of dissolved organic matter (DOM) in pore-water solutions have been confined mostly to recent sediments (Henrichs and Farrington, 1979; Krom and Sholkovitz, 1977; Nissenbaum et al., 1972). The analyses of organic constituents in interstitial waters have not been extended to sediment depths of more than 15 meters (Starikova, 1970). Large fluctuations in organic contents of near-bottom interstitial fluids suggest that organic compounds may provide insight into the chemical and biological processes occurring in the sedimentary column. Gradients in inorganic ion concentrations have been used as indicators of diagenesis of organic matter in deep sediments and interstitial waters. Shishkina (1978) attributed the occurrence of iodine and Cl/Br ratios that deviated from the value of seawater to the breakdown of organic matter and the liberation of bromide during mineralization. Sulfate depletion and maxima in ammonia concentrations were interpreted to be a consequence of sulfate reduction reactions in pore fluids, even at depths of more than 400 meters (Miller et al., 1979; Manheim and Schug, 1978).The purpose of this chapter is to study organic carbon compounds dissolved in interstitial waters of deep sediments at Sites 474 and 479.

Data on multidisciplinary research in the Tajura Rift (Gulf of Aden) during Cruise 7 of R/V Akademik Mstislav Keldysh in winter 1983-1984

In the collective monograph results of geological and geophysical studies in the Tadjura Rift carried out by conventional outboard instruments and from deep/sea manned submersibles "Pisces" in winter 1983-1984 are reported. Main features of rift tectonics, geology, petrology, and geochemistry of basalts from the rift are under consideration. An emphasis is made on lithology, stratigraphy, and geochemistry of bottom sediments. Roles of terrigenous, edafogenic, biogenic, and hydrothermal components in formation of bottom sediments from the rift zone are shown.