Concentration and isotope composition of sulphur in sediments and pore water at DSDP Leg 70 Holes

Data obtained while investigating the mounds area near the Galapagos Spreading Center demonstrate the direct influence of solutions derived from the interaction of seawater and young oceanic crust on the sedimentary cover. Investigation of metalliferous sediments from the mid-oceanic ridges, the Galapagos mounds, and the FAMOUS-area zone formations have shown that this influence and the resulting products are dependent on composition, temperature, and conditions of solution input. The study of sulfur in upwardly migrating solutions and the interaction of these solutions with sediments is of great interest. Investigations of different types of hydrothermally derived formations (Edmond, et al., 1979; Spiess et al., 1980; Styrt et al., 1981; Rosanova 1976; Grinenko et al., 1978) have shown the significant role of sulfur-bearing minerals in deposits formed from hightemperature solutions. In contrast, the addition of hydrothermal sulfur is negligible in those metalliferous sediments that precipitated as a result of the interaction between the solutions and open seawater (Bonatti et al., 1972, 1976; Gordeev et al., 1979; Migdisov, Bogdanov, et al., 1979). For example, sulfides are absent in clearly oxidized metalliferous sediments from the East Pacific Rise (EPR). Barite sulfur from these sediments is identical with seawater sulfate sulfur in isotope composition (Grinenko et al., 1978). Gurvich and Bogdanov (1977) have suggested that barium from EPR metalliferous sediments results completely from biological activity and from the components of ocean waters. Edmond et al. (1979) report that low-temperature springs from the Galapagos Rift axis contain two types of solutions: those with and those without H2S.

Strontium isotopic data for calcareous ooze, chalk, and pore waters from DSDP Hole 590B

A detailed study of strontium isotope variations in Neogene marine carbonate sediments from Deep Sea Drilling Project Site 590B, using techniques that allow the 87Sr/86Sr ratio to be determined to better than +/-0.00001, gives a high-resolution record of the Sr isotopic evolution of seawater. The data show that the rate of change of the marine 87Sr/86Sr ratio has varied significantly even on time scales as short as 1 m.y. Periods of particularly rapid growth appear to follow major marine regressions and probably reflect an increase in the delivery of radiogenic Sr from the continents coupled with a decreased submarine carbonate dissolution rate (greater carbonate compensation depth). Periods of relatively slowly changing 87Sr/86Sr follow major marine transgressions. On the basis of correlations with the marine oxygen isotope record and the times of major continental glacier growth, it is inferred that the effects of sea-level variations are modified by climatic factors that affect the intensity of continental weathering and runoff. The effects of sea-floor generation rate variations are not discernible for the Neogene. The maximum attainable stratigraphic resolution using Sr isotopes is between 0.1 and 2 m.y. for this time period.

(Table T2) Sulfur isotopes of pore water from ODP Leg 201 sites

Fifty-seven interstitial water samples from six sites (Ocean Drilling Program Sites 1225-1229 and 1231) in the eastern equatorial Pacific Ocean and the Peru margin were analyzed for the stable sulfur isotopic composition (34S/32S) of dissolved sulfate along with major and minor ions. With the exception of Site 1231, sulfate from the interstitial fluids (d34S values as much as 89 per mil vs. the SF6-based Vienna-Canyon Diablo troilite standard) is found at depth to be enriched in 34S with respect to modern seawater sulfate (d34S = ~21 per mil), indicating that microbial sulfate reduction (MSR) took place to different extents at all investigated sites. Deeper sediments at Sites 1228 and 1229 are additionally influenced by diffusion of a sulfate-rich brine that has already undergone sulfate reduction. The intensity of MSR depends on the availability of substrate (organic matter), sedimentation conditions, and the active bacterial community structure. Formation of isotopically heavy diagenetic barite at the sulfate-methane transition zone is expected at Sites 1227 (one front), 1229 (two fronts), and probably Site 1228. At Site 1231, the constant sulfur isotopic composition of sulfate and concentrations of minor pore water ions indicate that suboxic (essentially iron and manganese oxide based) diagenesis dominates and no net MSR occurs.

Geochemical and isotopic composition of sediments and pore waters from ODP Leg 164 sites

Authigenic carbonates were recovered from several horizons between 0 and 52 mbsf in sediments that overlay the Blake Ridge Diapir on the Carolina Rise (Ocean Drilling Program [ODP] Site 996). Active chemosynthetic communities at this site are apparently fed by fluid conduits extending beneath a bottom-simulating reflector (BSR). Gas hydrates occur at several depth intervals in these near-surface sediments. The carbonate nodules are composed of rounded to subangular intraclasts and carbonate cemented mussel shell fragments. Electron microprobe and X-ray diffraction (XRD) investigations show that aragonite is the dominant authigenic carbonate. Authigenic aragonite occurs both as microcrystalline, interstitial cement, and as cavity-filling radial fibrous crystals. The d13C values of the authigenic aragonite vary between -48.4 per mil and -30.5 per mil (Peedee belemnite [PDB]), indicating that carbon derived from 13C-depleted methane is incorporated into these carbonates. The d13C of pore water sum CO2 values are most negative in the upper 10 mbsf, near the sediment/water interface (-38 per mil ± 5 per mil), but noticeably more positive below 25 mbsf (+5 per mil ± 6 per mil). Because carbonates derive their carbon from HCO3-, dissimilarities between the d13C values of carbonate precipitates recovered from greater than 10 mbsf and d13C values of the associated pore fluids suggests that these carbonates formed near the seafloor. Differences of about 1 per mil in the oxygen isotopic composition of carbonate precipitates from different depths are possibly related to changes in bottom-water conditions during glacial and interglacial time periods. Measurements of the strontium isotopic composition on 13 carbonate samples show 87Sr/86Sr values between 0.709125 and 0.709206 with a mean of 0.709165, consistent with the approximate age of their host sediment. Furthermore, the 87Sr/86Sr values of six pore-water samples from Site 996 vary between 0.709130 and 0.709204. The similarity of these values to seawater (87Sr/86Sr = 0.709175), and to 87Sr/86Sr values of pore water from similar sample depths elsewhere on the Blake Ridge (Sites 994, 995, and 997), indicates a shallow Sr source. The 87Sr/86Sr values of the authigenic carbonates at Site 996 are not consistent with the Sr isotopic values predicted for carbonates precipitated from fluids transported upward along fault conduits extending through the base of the gas hydrate-stability zone. Based on our data, we see no evidence of continuing carbonate diagenesis with depth. Therefore, with the exception of their seafloor expression as carbonate crusts, fossil vent sites will not be preserved. Because these authigenic features apparently form only at the seafloor, their vertical distribution and sediment age imply that seepage has been going on in this area for at least 600,000 yr.

Lithium and strontium isotopic compositions of sediments and pore waters at ODP Sites 152-918 and 152-919

The distribution of Li isotopes in pore waters to a depth of 1157 m below seafloor is presented for ODP Sites 918 and 919 in the Irminger Basin, offshore Greenland. Lithium isotope data are accompanied by strontium isotope ratios to decipher diagenetic reactions in the sediments which are characterized by the pervasive presence of volcanic material, as well as by very high accumulation rates in the upper section. The lowering of the 87Sr/86Sr ratio below contemporaneous seawater values indicates several zones of volcanic material alteration. The Li isotope profiles are complex suggesting a variety of exchange reactions with the solid phases. These include cation exchange with NH4+ and mobilization from sediments at depth, in addition to the alteration of volcanic matter. Lithium isotopes are, therefore, a sensitive indicator of sediment-water interaction. d6Li values of pore waters at these two sites vary between -42 and -25?. At shallow depths (<100 mbsf), rapid decreases in the Li concentration, accompanied by a shift to heavier isotopic compositions, indicate uptake of Li into alteration products. A positive anomaly of d6Li observed at both sites is coincident with the NH4+ maximum produced by organic matter decomposition and may be related to ion exchange of Li from the sediments by NH4+. In the lower sediment column at Site 918, dissolved Li increases with depth and is characterized by enrichment of 6Li. The Li isotopic compositions of both the waters and the solid phase suggest that the enrichment of Li in deep interstitial waters is a result of release from pelagic sediments. The significance of sediment diagenesis and adsorption as sinks of oceanic Li is evaluated. The maximum diffusive flux into the sediment due to volcanic matter alteration can be no more than 5% of the combined inputs from rivers and submarine hydrothermal solutions. Adsorption on to sediments can only account for 5-10% of the total inputs from rivers and submarine hot springs.

Pore water and sediment geochemistry of the Bothian Sea

Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

Composition of hardgrounds and of pore-water parameters in ODP Holes 166-1008 and 166-1009

Mineralogic, petrographic, and geochemical analyses of sediments recovered from two Leg 166 Ocean Drilling Program cores on the western slope of Great Bahama Bank (308 m and 437 m water depth) are used to characterize early marine diagenesis of these shallow-water, periplatform carbonates. The most pronounced diagenetic products are well-lithified intervals found almost exclusively in glacial lowstand deposits and interpreted to have formed at or near the seafloor (i.e., hardgrounds). Hardground cements are composed of high-Mg calcite (~14 mol% MgCO3), and exhibit textures typically associated with seafloor cementation. Geochemically, hardgrounds are characterized by increased d18O and Mg contents and decreased d13C, Sr, and Na contents relative to their less lithified counterparts. Despite being deposited in shallow waters that are supersaturated with the common carbonate minerals, it is clear that these sediments are also undergoing shallow subsurface diagenesis. Calculation of saturation states shows that pore waters become undersaturated with aragonite within the upper 10 m at both sites. Dissolution, and likely recrystallization, of metastable carbonates is manifested by increases in interstitial water Sr and Sr/Ca profiles with depth. We infer that the reduction in mineral saturation states and subsequent dissolution are being driven by the oxidation of organic matter in this Fe-poor carbonate system. Precipitation of burial diagenetic phases is indicated by the down-core appearance of dolomite and corresponding decrease in interstitial water Mg, and the presence of low-Mg calcite cements observed in scanning electron microscope photomicrographs.

Sediment and pore fluid chemistry for IODP Sites 311-U1325 and 311-U1329

Analytical challenges in obtaining high quality measurements of rare earth elements (REEs) from small pore fluid volumes have limited the application of REEs as deep fluid geochemical tracers. Using a recently developed analytical technique, we analyzed REEs from pore fluids collected from Sites U1325 and U1329, drilled on the northern Cascadia margin during the Integrated Ocean Drilling Program (IODP) Expedition 311, to investigate the REE behavior during diagenesis and their utility as tracers of deep fluid migration. These sites were selected because they represent contrasting settings on an accretionary margin: a ponded basin at the toe of the margin, and the landward Tofino Basin near the shelf's edge. REE concentrations of pore fluid in the methanogenic zone at Sites U1325 and U1329 correlate positively with concentrations of dissolved organic carbon (DOC) and alkalinity. Fractionations across the REE series are driven by preferential complexation of the heavy REEs. Simultaneous enrichment of diagenetic indicators (DOC and alkalinity) and of REEs (in particular the heavy elements Ho to Lu), suggests that the heavy REEs are released during particulate organic carbon (POC) degradation and are subsequently chelated by DOC. REE concentrations are greater at Site U1325, a site where shorter residence times of POC in sulfate-bearing redox zones may enhance REE burial efficiency within sulfidic and methanogenic sediment zones where REE release ensues. Cross-plots of La concentrations versus Cl, Li and Sr delineate a distinct field for the deep fluids (z > 75 mbsf) at Site U1329, and indicate the presence of a fluid not observed at the other sites drilled on the Cascadia margin. Changes in REE patterns, the presence of a positive Eu anomaly, and other available geochemical data for this site suggest a complex hydrology and possible interaction with the igneous Crescent Terrane, located east of the drilled transect.

Pore-water chemistry of abyssal Arabian Sea surface sediments

Benthic fluxes and pore-water compositions of silicic acid, nitrate and phosphate were investigated for surface sediments of the abyssal Arabian Sea during four cruises (1995-1998). Five sites located in the northern (NAST), western (WAST), central (CAST), eastern (EAST), and southern (SAST) Arabian Sea were revisited during intermonsoonal periods after the NE- and SW-Monsoon. At these sites, benthic fluxes of remineralized nutrients from the sediment to the bottom water of 36-106, 102-350 and 4-16 mmol/m**2/yr were measured for nitrate, silicic acid and phosphate, respectively. The benthic fluxes and pore-water compositions showed a distinct regional pattern. Highest fluxes were observed in the western and northern region of the Arabian Sea, whereas decreasing fluxes were derived towards the southeast. At WAST, the general temporal pattern of primary production, related to the NE- and SW-Monsoon, is reflected by benthic fluxes. In contrast, at sites NAST, SAST, CAST, and EAST a temporal pattern of fluxes in response to the monsoon is not obvious. Our results reveal a clear coupling between the general regional pattern of production in surface waters and the response of the benthic environment, as indicated by the flux of remineralized nutrients, though a spatially differing degree of decoupling during transport and remineralization of particulate organic matter and biogenic opal was observed. This has to be taken into account regarding budget calculations and paleoceanographic topics.

Strontium and neodymium concentrations and isotope compositions in fossil fish teeth and pore waters at ODP Sites 130-807 and 125-786

We analyzed Nd and Sr isotopic compositions of Neogene fossil fish teeth from two sites in the Pacific in order to determine the effect of cleaning protocols and burial diagenesis on the preservation of seawater isotopic values. Sr is incorporated into the teeth at the time of growth; thus Sr isotopes are potentially valuable for chemostratigraphy. Nd isotopes are potential conservative tracers of paleocirculation; however, Nd is incorporated post-mortem, and may record diagenetic pore waters rather than seawater. We evaluated samples from two sites (Site 807A, Ontong Java Plateau and Site 786A, Izu-Bonin Arc) that were exposed to similar bottom waters, but have distinct lithologies and pore water chemistries. The Sr isotopic values of the fish teeth appear to accurately reflect contemporaneous seawater at both sites. The excellent correlation between the Nd isotopic values of teeth from the two sites suggests that the Nd is incorporated while the teeth are in chemical equilibrium with seawater, and that the signal is preserved over geologic timescales and subsequent burial. These data also corroborate paleoseawater Nd isotopic compositions derived from Pacific ferromanganese crusts that were recovered from similar water depths (Ling et al., 1997; doi:10.1016/S0012-821X(96)00224-5). This corroboration strongly suggests that both materials preserve seawater Nd isotope values. Variations in Pacific deepwater e-Nd values are consistent with predictions for the shoaling of the Isthmus of Panama and the subsequent initiation of nonradiogenic North Atlantic Deep Water that entered the Pacific via the Antarctic Circumpolar Current.

Carbon isotopic composition and dissolved CO2 concentration in pore waters of ODP Leg 174A sites

Microbially mediated redox diagenetic processes in marine sediments are reflected in the amount and carbon isotopic composition of dissolved CO2 and CH4 (Claypool and Kaplan, 1974). Oxidation of organic matter gives rise to dissolved CO2 with about the same 13C/12C ratio as the starting organic matter. Subsequent reduction of CO2 to form CH4 involves a large (~70) kinetic isotopic effect, resulting in significant 13C depletion in the CH4, and 13C enrichment in the residual CO2. Ocean Drilling Program Leg 174A (offshore New Jersey) presented an opportunity to study these processes in shelf and upper slope sediments. Holes 1071A-1071D, 1071F, and 1072A were drilled on the shelf in water depths of 88.0-98.1 m. Hole 1073A was drilled on the slope in 639.4 m of water. Pore-water samples were collected for analysis at all three sites, whereas gas samples could only be obtained from Hole 1073A on the slope.

Strontium isotopes in pore waters of east equatorial Pacific sediments

Pore-water samples from the equatorial sedimentary bulge area show reversals in depth profiles of 87Sr/86Sr ratios at the sediment/basement interface. Results of this work support inferences made from previous pore-water data (from DSDP drilling in the area) that large-scale horizontal advection of seawater has occurred through the basement underlying the thick sedimentary sequence in this region. The area of apparent advection includes the eastern part of the equatorial high-productivity zone and part of the Guatemala Basin. We attempted to find links between the observed near-basement reversals in pore-water chemistry and sedimentary thickness, age, and topography of the area. Most of the sites that show horizontal advection have disturbed basement topography or outcrops within 10 to 20 km, suggesting that the cooling effects of outcrops may extend for at least 20 km horizontally. Heat-flow data from the area were compared to determine whether sites showing near-bottom chemistry reversals were consistent with areas of low conductive heat flow. This was generally true for the area of the sedimentary bulge and Guatemala Basin. Not enough pore-water data from the Nazca Plate were available to establish any reliable systematics. Because the high-productivity area is well-sealed from hydrothermal circulation, the missing heat must be lost by horizontal advective heat transport. From profiles of strontium isotopes and other elements that show departure from seawater values with increasing depth in the sediments, but return to seawater values near the basement, it appears that water flows relatively freely through much of the oceanic crust, even when sealed by considerable sedimentary cover.

Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of the Integrated Ocean Drilling Program (IODP) expedition 313 "New Jersey Shallow Shelf" were analyzed for chemical composition and stable isotope ratios. A total of 222 water samples were collected from the cores by Rhizon samplers and squeezing of fresh core material. Water was analyzed for its stable oxygen and hydrogen isotope geochemistry (d2H and d18O) at sites M0027A and M0029A, and the carbon isotope composition of the dissolved inorganic carbon (d13CDIC) (all sites). In addition, organic material (Corg) and inorganic carbonates from sediments were analyzed for their carbon ratios (d13Corg and d13Ccarb), and in case of the carbonates also for oxygen (d18Ocarb). Carbon isotopes were also analyzed in samples containing enough methane gas (d13Cmeth). Pore fluids from site M0027A were analyzed for the sulfur isotope composition of dissolved sulfate (d34S). The combination of isotope analyses of all phases (interstitial water, sediment, and gas) with pore water chemistry is expected to enable a better understanding of processes in the sediment and will help to identify the origin of fluids under the New Jersey shelf.