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.

Sulphur geochemistry of interstitial waters and squeeze cake samples of ODP Leg 181 sites

Seventy-nine interstitial water samples from six sites (Ocean Drilling Program Sites 1119-1124) from the southwestern Pacific Ocean have been analyzed for stable isotopes of dissolved sulfate (34S), along with major and minor ions. Sulfate from the interstitial fluids (34S values between +20.7 and +57.5 vs. the Vienna-Canyon Diablo troilite standard) was enriched in 34S with respect to modern seawater (34S +20.6), indicating that differing amounts of microbial sulfate reduction took place at all investigated sites. Microbial sulfate reduction was found at all sites, the intensity depending on the availability of organic matter, which is controlled by paleosedimentation conditions (e.g., sedimentation rate and presence of turbidites). In addition, total reduced inorganic sulfur (essentially pyrite) as a product of microbial sulfate reduction was quantified in selected sediments from Site 1119.

Biogeochemical investigation of cold seep sediments in the Eastern Mediterranean Sea

Cold seep ecosystems are highly productive, fragmented ecosystems of the deep-sea floor. They form worldwide where methane reaches the surface seafloor, and are characterized by rich chemosynthetic communities fueled by the microbial utilization of hydrocarbons. Here we investigated with in situ (benthic chamber, microprofiler) and ex situ (pore water constituents, turnover rates of sulfate and methane, prokaryote abundance) techniques reduced sites from three different seep ecosystems in the Eastern Mediterranean deep-sea. At all three cold seep systems, the Amon Mud Volcano, Amsterdam Mud Volcano and the Nile Deep Sea Fan Pockmark area, we observed and sampled patches of highly reduced, methane-seeping sulfidic sediments which were separated by tens to hundreds of (kilo)meters with non-reduced oxygenated seafloor areas. All investigated seep sites were characterized by gassy, sulfidic sediments of blackish color, of which some were overgrown with thiotrophic bacterial mats. Fluxes of methane and oxygen, as well as sulfate reduction rates varied between the different sites.

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.

Geochemistry of middle Eocene-lower Oligocene pelagic sediments of ODP Hole 105-647A

Geochemical analyses of the middle Eocene through lower Oligocene lithologic Unit IIIC (260-518 meters below seafloor [mbsf]) indicate a relatively constant geochemical composition of the detrital fraction throughout this depositional interval at Ocean Drilling Program (ODP) Site 647 in the southern Labrador Sea. The main variability occurs in redox-sensitive elements (e.g., iron, manganese, and phosphorus), which may be related to early diagenetic mobility in anaerobic pore waters during bacterial decomposition of organic matter. Initial preservation of organic matter was mediated by high sedimentation rates (36 m/m.y.). High iron (Fe) and manganese (Mn) contents are associated with carbonate concretions of siderite, manganosiderite, and rhodochrosite. These concretions probably formed in response to elevated pore-water alkalinity and total dissolved carbon dioxide (CO2) concentrations resulting from bacterial sulfate reduction, as indicated by nodule stable-isotope compositions and pore-water geochemistry. These nodules differ from those found in upper Cenozoic hemipelagic sequences in that they are not associated with methanogenesis. Phosphate minerals (carbonate-fluorapatite) precipitated in some intervals, probably as the result of desorption of phosphorus from iron and manganese during reduction. The bulk chemical composition of the sediments differs little from that of North Atlantic Quaternary abyssal red clays, but may contain a minor hydrothermal component. The silicon/ aluminum (Si/Al) ratio, however, is high and variable and probably reflects original variations in biogenic opal, much of which is now altered to smectite and/or opal CT. An increase in the sodium/potassium (Na/K) ratio in the upper Eocene corresponds to the beginning of coarsergrained feldspar flux to the site, possibly marking the onset of more vigorous deep currents. Although the Site 647 cores provide a nearly complete high-resolution, high-latitude Eocene-Oligocene record, the high sedimentation rate and somewhat unusual diagenetic conditions have led to variable alteration of benthic foraminifers and fine-fraction carbonate and have overprinted the original stable-isotope records. Planktonic foraminifers are less altered, but on the whole, there is little chance of sorting out the nature and timing of environmental change on the basis of our stable-isotope analyses.

Magnetic properties of light and dark sediment layers from the Japan Sea

Rock magnetic/paleoclimatic/diagenetic relationships of sediments spanning the last 0.78 Ma have been investigated using samples collected from light and dark layers recovered at ODP Sites 794 (Yamato Basin) and 795 (Japan Basin). Rock-magnetic parameters (K, Kfd, ARM, SIRM, S-ratio) are shown to reflect diagenetic processes and climate-related variations in the concentration, mineralogy and grain-size of the magnetic minerals contained within the sediments. The magnetic mineralogy is dominated by ferrimagnetic (magnetite-type) minerals with a small contribution made by hematite and iron sulphides such as pyrrhotite and/or greigite. Magnetic mineral concentration and grain size vary between light and dark layers with the former characterized by a higher magnetic content and a finer magnetic grain size. Magnetite dissolution, related to sulfate reduction due to bacterial degradation of organic matter, is the process responsible for the magnetic characteristics observed in the dark layers, testifying to the reducing conditions in the basin. Variations in the rock magnetic properties of the sediments are strongly correlated with global oxygen isotope fluctuations, with glacial stages characterized by a lower magnetic mineral content and a coarser magnetic grain size relative to interglacial stages. Major downcore changes in the magnetic properties observed at Site 794 can be related to changes in the oceanographic conditions of the basin associated with the flow of the warm Tsushima Current into the Japan Sea at about 0.35-0.40 Ma ago.

Sulphur chemistry of the ODP Site 206-1256 volcanic section

Sulfide mineralogy and the contents and isotope compositions of sulfur were analyzed in a complete oceanic volcanic section from IODP Hole 1256D in the eastern Pacific, in order to investigate the role of microbes and their effect on the sulfur budget in altered upper oceanic crust. Basalts in the 800 m thick volcanic section are affected by a pervasive low-temperature background alteration and have mean sulfur contents of 530 ppm, reflecting loss of sulfur relative to fresh glass through degassing during eruption and alteration by seawater. Alteration halos along fractures average 155 ppm sulfur and are more oxidized, have high SO4/Sum S ratios (0.43), and lost sulfur through oxidation by seawater compared to host rocks. Although sulfur was lost locally, sulfur was subsequently gained through fixation of seawater-derived sulfur in secondary pyrite and marcasite in veins and in concentrations at the boundary between alteration halos and host rocks. Negative d34S[sulfide-S] values (down to -30 per mil) and low temperatures of alteration (down to ~40 °C) point to microbial reduction of seawater sulfate as the process resulting in local additions of sulfide-S. Mass balance calculations indicate that 15-20% of the sulfur in the volcanic section is microbially derived, with the bulk altered volcanic section containing 940 ppm S, and with d34S shifted to -6.0 per mil from the mantle value (0 per mil). The bulk volcanic section may have gained or lost sulfur overall. The annual flux of microbial sulfur into oceanic basement based on Hole 1256D is 3-4 * 10**10 mol S/yr, within an order of magnitude of the riverine sulfate source and the sedimentary pyrite sink. Results indicate a flux of bacterially derived sulfur that is fixed in upper ocean basement of 7-8 * 10**-8 mol/cm**-2/yr1 over 15 m.y. This is comparable to that in open ocean sediment sites, but is one to two orders of magnitude less than for ocean margin sediments. The global annual subduction of sulfur in altered oceanic basalt lavas based on Hole 1256D is 1.5-2.0 * 10**11 mol/yr, comparable to the subduction of sulfide in sediments, and could contribute to sediment-like sulfur isotope heterogeneities in the mantle.

Sulfur speciation in bottom sediments from the Peru upwelling area

Sulfur speciation in bottom sediments from the area of the Peru upwelling has been studied. Data on sulfur contents in different compounds (sulfide, elemental, sulfate, pyritic and organic), water content, Eh, and organic carbon content in the bottom sediments have been obtained. The bottom sediments from the area are characterized by high content of organic carbon and low contents of total and reactive iron; this is typical for bottom sediments from ocean upwelling areas. Intense process of sulfate reduction occurs in the bottom sediments of the area, and accumulation of reduced sulfur compounds derivated from bacterial hydrogen sulfide does not exceed previously known values for other regions of the ocean.

Methane and sulfide fluxes in permanent anoxia: in situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV), located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea), was visited during the M72/2 cruise with the RV Meteor to investigate the methane and sulfide release from mud volcanoes into the Black Sea hydrosphere. We studied benthic fluxes of methane and sulfide, and the factors controlling transport, consumption and production of both compounds within the sediment. The pie shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at a small elevation north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was excluded from this zone due to fluid-flow induced sulfate limitation and a fresh mud flow and consequently methane escaped into the water column with a rate of 0.46 mol/m**2/d. In the outer center of the mud volcano fluid flow and total methane flux were decreased, correlating with an increase in sulfate penetration into the sediment, and with higher SR and AOM rates. Here between 50-70% of the methane flux (0.07-0.1 mol/m**2/d) was consumed within the upper 10 cm of the sediment. Also at the edge of the mud volcano fluid flow and rates of methane and sulfate turnover were substantial. The overall amount of dissolved methane released from the mud volcano into the water column was significant with a discharge of 1.4x10**7 mol/yr. The DMV maintains also high areal rates of methane-fueled sulfide production of on average 0.05 mol/m**2/d. However, we concluded that sulfide and methane emission into the hydrosphere from deep water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.

Magnetic properties of two cores from the Iberian Margin

Magnetic properties of late Quaternary sediments on the SW Iberian Margin are dominated by bacterial magnetite, observed by transmission electron microscopy (TEM), with contributions from detrital titanomagnetite and hematite. Reactive hematite from eolian dust, together with low organic matter concentrations and the lack of sulfate reduction, lead to dissimilatory iron reduction and availability of Fe(II) for abundant magnetotactic bacteria. Magnetite grain-size proxies (kARM/k and ARM/IRM) and S-ratios (sensitive to hematite) vary on stadial/interstadial timescales, contain orbital power, and mimic planktic d18O. The detrital/biogenic magnetite ratio and hematite concentration are greater during stadials and glacial isotopic stages, reflecting increased detrital (magnetite) input during times of lowered sea level, coinciding with atmospheric conditions favoring hematitic dust supply. Magnetic susceptibility, on the other hand, has a very different response being sensitive to coarse detrital multidomain (MD) magnetite associated with ice-rafted debris (IRD). High susceptibility and/or magnetic grain size coarsening, mark Heinrich stadials (HS), particularly HS2, HS3, HS4, HS5, HS6 and HS7, as well as older Heinrich-like detrital layers, indicating the sensitivity of this region to fluctuations in the position of the polar front. Relative paleointensity (RPI) records have well-constrained age models based on planktic d18O correlation to ice-core chronologies, however, they differ from reference records (e.g. PISO) particularly in the vicinity of glacial maxima, mainly due to inefficient normalization of RPI records in intervals of enhanced detrital/eolian hematite input.

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The ultramafic-hosted Logatchev hydrothermal field (LHF) is characterized by vent fluids, which are enriched in dissolved hydrogen and methane compared with fluids from basalt-hosted systems. Thick sediment layers in LHF are partly covered by characteristic white mats. In this study, these sediments were investigated in order to determine biogeochemical processes and key organisms relevant for primary production. Temperature profiling at two mat-covered sites showed a conductive heating of the sediments. Elemental sulfur was detected in the overlying mat and metal-sulfides in the upper sediment layer. Microprofiles revealed an intensive hydrogen sulfide flux from deeper sediment layers. Fluorescence in situ hybridization showed that filamentous and vibrioid, Arcobacter-related Epsilonproteobacteria dominated the overlying mats. This is in contrast to sulfidic sediments in basalt-hosted fields where mats of similar appearance are composed of large sulfur-oxidizing Gammaproteobacteria. Epsilonproteobacteria (7- 21%) and Deltaproteobacteria (20-21%) were highly abundant in the surface sediment layer. The physiology of the closest cultivated relatives, revealed by comparative 16S rRNA sequence analysis, was characterized by the capability to metabolize sulfur com- ponents. High sulfate reduction rates as well as sulfide depleted in 34S further confirmed the importance of the biogeochemical sulfur cycle. In contrast, methane was found to be of minor relevance for microbial life in mat-covered surface sediments. Our data indicate that in conductively heated surface sediments microbial sulfur cycling is the driving force for bacterial biomass production although ultramafic- hosted systems are characterized by fluids with high levels of dissolved methane and hydrogen.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

Amino acids in the interstitial waters from ODP Hole 113-695A

Site 695 lies on the southeast margin of the South Orkney microcontinent on the northern margin of the Weddell Sea, at 62°23.48'S, 43°27.10'W in 1305 m water depth. The inorganic properties of interstitial waters at this site, including sulfate reduction, biogenic methane production, and high concentrations of ammonia and phosphate, imply high microbial activity. However, no clear relationship between amino acid composition and concentration and the type of microbial activity (e.g., sulfate reduction or methane production) can be identified. The THAA (total hydrolyzable amino acids) values range between 2.45 and 17.31 µmol/L, averaging 7.14 µmol/L. The mean concentrations and relative abundance values of acidic, basic, neutral, aromatic, and sulfur-containing amino acids are 1.34 (18%), 1.09 (15%), 3.93 (54%), 0.50 (8%), and 0.02 (0%) µmol/L, respectively. Glycine is the most abundant amino acid residue, with serine, glutamic acid, and ornithine next. The DFAA (dissolved free amino acids) values range from 0.10 to 12.73 µmol/L, averaging 4.07 µmol/L. The acidic, basic, neutral, aromatic, and sulfurcontaining amino acids are on average 0.21, 0.79, 2.56, 0.41, and 0.01 µmol/L, respectively. The relative abundances of acidic, basic, neutral, and aromatic amino acids average 4%, 18%, 58%, and 15%, respectively. Predominance of DFAA over DCAA (dissolved combined amino acids) in interstitial waters of Lithologic Units I and II is contrary to the predominance of DCAA over DFAA in other interstitial waters and seawater. The comparison of amino acid compositions between DCAA and siliceous plankton suggests that the DCAA in interstitial waters originally comes from amino acids derived from siliceous plankton. However, other sources which are much enriched in glutamic acid contribute to the DCAA composition.