Pore-water chemistry of ODP sites 111-677 and 111-678

Sites 677 and 678 were drilled on ODP Leg 111 to test hypotheses about the nature and pattern of hydrothermal circulation on a mid-ocean ridge flank. Together with earlier results from DSDP Site 501/504 and several heatflow and piston coring surveys covering a 100-km**2 area surrounding the three drill sites, they confirm that hydrothermal circulation persists in this 5.9-m.y.-old crust, both in basement and through the overlying sediments (Langseth et al., 1988, doi:10.2973/odp.proc.ir.111.102.1988). Profiles of sediment pore-water composition with depth at the three drill sites show both vertical and horizontal gradients. The shapes of the profiles and their variation from one site to another result from a combination of vertical and horizontal diffusion, convection, and reaction in the sediments and basement. Chemical species that are highly reactive in the siliceous-calcareous biogenic sediments include bicarbonate (alkalinity), ammonium, sulfate, manganese, calcium, strontium, lithium, silica, and possibly potassium. Reactions include bacterial sulfate reduction, mobilization of Mn2+, precipitation of CaCO3, and recrystallization of calcareous and siliceous oozes to chalk, limestone, and chert. Species with profiles more affected by reaction in basaltic basement than in the sediments include Mg, Ca, Na, K, and oxygen isotopes. Reaction in basement at 60?C and at higher temperatures has produced a highly altered basement formation water that is uniform in composition over distances of several kilometers. As inferred from the composition of the basal sediment pore water at the three sites, this uniformity extends from up flow zone to downflow zone in basement and the sediments. It exists in spite of large variations in heat flow and depth to basement, apparently as a result of homogenization by hydrothermal circulation in basement. Profiles for chlorinity, Na, Mg, and other species in the sediment pore waters confirm that Site 678, drilled on a localized heatflow high identified by Langseth et al. (1988), is a site of long-lived upwelling of warm water from basement through the sediments at velocities of 1 to 2 mm/yr. The upflow through the anomalously thin sediments is apparently localized above an uplifted fault block in basement. This site and other similar sites in the survey area give rise to lateral diffusion and possibly flow through the sediments, which produces lateral gradients in sediment pore-water composition at sites such as 501/504. The complementary pore-water profiles at the low-heatflow Site 677 2 km to the south indicate that downflow is occurring through the sediments there, at comparable rates of 1 to 2 mm/yr.

Benthic foraminifera in sapropels of the eastern Mediterranean Sea

High-resolution benthic foraminiferal and geochemical investigations were carried out across sapropels S5 and S6 from two sediment cores in the Levantine Sea to evaluate the impact of climatic and environmental changes on benthic ecosystems during times of sapropel formation. The faunal successions indicate that eutrophication and/or oxygen reduction started several thousand years prior to the onset of sapropel formation, suggesting an early response of the bathyal ecosystems to climatic changes. Severest oxygen depletions appear in the early phases of sapropel formation. The initial reduction of deep-water ventilation is caused by a warming and fresh water-induced stratification of Eastern Mediterranean surface waters. During the late phase of S5 formation improved oxygenation is restricted to middle bathyal ecosystems, indicating that at least some formation of subsurface water took place. During S6 formation oxygen depletions and eutrophication were less severe and more variable than during S5 formation. Estimated oxygen contents were low dysoxic at middle bathyal to anoxic at lower bathyal depths during the early phase of S6 formation but never dropped to anoxic values in its late phase. The high benthic ecosystem variability during S6 formation suggests that water column stratification at deep-water formation sites was in a very unstable mode and susceptible to minor temperature fluctuations at a millennial time-scale.

Geochemistry of recent marine sediments, interstitial water, and sea water from the West African continental margin

Carbon dioxide, ammonia, and reactive phosphate in the interstitial water of three sediment cores of the West African continental margin result from oxidation of sedimentary organic matter by bacterial sulfate reduction. The proposed model is a modification of one initially suggested by Richards (1965) for processes in anoxic waters: (CH2O)106 (NH3)8 (H3PO4) (0.7-0.2) + 53 SO4**2- =106 CO2 + 106 H20 + 8 NH3 + (0.7 - 0.2) H3PO4 + 53 S**2- The amount of reduced interstitial sulfate, the carbon-to-nitrogen-to-phosphorus atomic ratio of the sedimentary organic matter, as well as small amounts of carbon dioxide, which precipitated as interstitial calcium carbonate, are included in the general oxidation-reduction reaction. Preferential loss of nitrogen and phosphorus from organic matter close to the surface was recorded in both the interstitial water and sediment composition. It appeared that in deeper sections of the core organic carbon compounds were oxidized which were probably in an even lower oxidation state than that indicated by the proposed model. An estimated 2 % of the amount of organic matter still present was oxidized after it became incorporated into the sediment; whereas sulfide sulfur contents indicate that a much larger percentage (15-20%) seemed to have been subject to bacterial oxidation during the Pleistocene period, when a very thin oxidizing layer on the sediment allowed the above decomposition process to start relatively early favoured by almost fresh organic matter, and by almost unrestricted exchange of sulfate with the overlying water.

Oxygen and sulfur isotopes of peridotite and gabbro from the Mid-Atlantic Ridge

Whole rock sulfur and oxygen isotope compositions of altered peridotites and gabbros from near the 15°20'N Fracture Zone on the Mid-Atlantic Ridge were analyzed to investigate hydrothermal alteration processes and test for a subsurface biosphere in oceanic basement. Three processes are identified. (1) High-temperature hydrothermal alteration (~250-350°C) at Sites 1268 and 1271 is characterized by 18O depletion (2.6-4.4 per mil), elevated sulfide-S, and high delta34S (up to ~2 wt% and 4.4-10.8 per mil). Fluids were derived from high-temperature (>350°C) reaction of seawater with gabbro at depth. These cores contain gabbroic rocks, suggesting that associated heat may influence serpentinization. (2) Low-temperature (<150°C) serpentinization at Sites 1272 and 1274 is characterized by elevated delta18O (up to 8.1 per mil), high sulfide-S (up to ~3000 ppm), and negative delta34S (to -32.1 per mil) that reflect microbial reduction of seawater sulfate. These holes penetrate faults at depth, suggesting links between faulting and temperatures of serpentinization. (3) Late low-temperature oxidation of sulfide minerals caused loss of sulfur from rocks close to the seafloor. Sulfate at all sites contains a component of oxidized sulfide minerals. Low delta34S of sulfate may result from kinetic isotope fractionation during oxidation or may indicate readily oxidized low-delta34S sulfide derived from microbial sulfate reduction. Results show that peridotite alteration may be commonly affected by fluids +/- heat derived from mafic intrusions and that microbial sulfate reduction is widespread in mantle exposed at the seafloor.

Oxygen microprofiles and porewater chemistry in sediments of the Skagerrak

Sediment porewater oxygen profiles were measured with micro and needle electrodes in sediment cores of 27 stations in the Skagerrak (northeastern North Sea). Oxygen penetration depth ranged from 3 to 20 mm depth. Fluxes estimated from the oxygen gradients varied from 3 to 18 mmol m**-2 d**-1. Oxygen penetration and flux depend on water depth, but possibly more on the hydrological conditions, related to the import of fresh organic matter by primary production in the water column. Oxygen fluxes were not related to the total organic carbon (TOC) content of the sediments. Stations in the eastern part of the Skagerrak showed high burial rates of TOC. At 6 stations porewater chemistry of Fe, Mn and NO3- was strongly associated with the oxygen distribution. The average relative contribution of terminal electron acceptors to carbon mineralisation was estimated at 85% for O2, 0.5% for Mn, 4.5% for [NO3]3-, 1% for Fe and 9% for [SO4]2-. At one station the occurrence of exceptionally high solid manganese oxyhydroxides was probably related to an active internal manganese cycle.

Planktonic foraminifera in the latest Maastrichtian of Walvis Ridge, South Atlantic

An abrupt global warming of 3-4°C occurred near the end of the Maastrichtian at 65.45-65.10 Ma. The environmental effects of this warm event are here documented based on stable isotopes and quantitative analysis of planktonic foraminifera at the South Atlantic DSDP Site 525A. Stable isotopes of individual species mark a rapid increase in temperature and a reduction in the vertical water mass stratification that is accompanied by a decrease in niche habitats, reduced species diversity and/or abundance, smaller species morphologies or dwarfing, and reduced photosymbiotic activity. During the warm event, the relative abundance of a large number of species decreased, including tropical-subtropical affiliated species, whereas typical mid-latitude species retained high abundances. This indicates that climate warming did not create favorable conditions for all tropical-subtropical species at mid-latitudes and did not cause a massive retreat in the local mid-latitude population. A noticeable exception is the ecological generalist Heterohelix dentata Stenestad that dominated during the cool intervals, but significantly decreased during the warm event. However, dwarfing is the most striking response to the abrupt warming and occurred in various species of different morphologies and lineages (e.g. biserial, trochospiral, keeled globotruncanids). Dwarfing is a typical reaction to environmental stress conditions and was likely the result of increased reproduction rates. Similarly, photosymbiotic activity appears to have been reduced significantly during the maximum warming, as indicated by decreased delta13C values. The foraminiferal response to climate change is thus multifaceted resulting in decreased species diversity, decreased species populations, increased competition due to reduced niche habitats, dwarfing and reduced photosymbiotic activity.

Chemistry of sediment profile GeoB4906

Mineralization of organic matter and the subsequent dissolution of calcite were simulated for surface sediments of the upper continental slope off Gabon by using microsensors to measure O2, pH, pCO2 and Ca2+ (in situ), pore-water concentration profiles of NO3-, NH4+, Fe2+, and Mn2+ and SO42- (ex situ), as well as sulfate reduction rates derived from incubation experiments. The transport and reaction model CoTReM was used to simulate the degradation of organic matter by O2, [NO3]-, Fe(OH)3 and [SO4]2-, reoxidation reactions involving Fe2+ and Mn2+, and precipitation of FeS. Model application revealed an overall rate of organic matter mineralization amounting to 50 µmol C cm**-2 yr**-1, of which 77% were due to O2, 17% to [NO3]- and 3% to Fe(OH)3 and 3% to [SO4]2-. The best fit for the pH profile was achieved by adapting three different dissolution rate constants of calcite ranging between 0.01 and 0.5% d-1 and accounting for different calcite phases in the sediment. A reaction order of 4.5 was assumed in the kinetic rate law. A CaCO3 flux to the sediment was estimated to occur at a rate of 42 g m**-2 yr**-1 in the area of equatorial upwelling. The model predicts a redissolution flux of calcite amounting to 36 g m**-2 yr**-1, thus indicating that ~90% of the calcite flux to the sediment is redissolved.

Element contents, sulfur and oxygen isotopes, and molecular biomarkers of phosphatic crust samples from the Chimbote Platform of the shelf off Peru

Authigenic phosphatic laminites enclosed in phosphorite crusts from the shelf off Peru (10°01' S and 10°24' S) consist of carbonate fluorapatite layers, which contain abundant sulfide minerals including pyrite (FeS2) and sphalerite (ZnS). Low d34Spyrite values (average -28.8 per mill) agree with bacterial sulfate reduction and subsequent pyrite formation. Stable sulfur isotopic compositions of sulfate bound in carbonate fluorapatite are lower than that of sulfate from ambient sea water, suggesting bacterial reoxidation of sulfide by sulfide-oxidizing bacteria. The release of phosphorus and subsequent formation of the autochthonous phosphatic laminites are apparently caused by the activity of sulfate-reducing bacteria and associated sulfide-oxidizing bacteria. Following an extraction-phosphorite dissolution-extraction procedure, molecular fossils of sulfate-reducing bacteria (mono-O-alkyl glycerol ethers, di-O-alkyl glycerol ethers, as well as the short-chain branched fatty acids i/ai-C15:0, i/ai-C17:0 and 10MeC16:0) are found to be among the most abundant compounds. The fact that these molecular fossils of sulfate-reducing bacteria are distinctly more abundant after dissolution of the phosphatic laminite reveals that the lipids are tightly bound to the mineral lattice of carbonate fluorapatite. Moreover, compared with the autochthonous laminite, molecular fossils of sulfate-reducing bacteria are: (1) significantly less abundant and (2) not as tightly bound to the mineral lattice in the other, allochthonous facies of the Peruvian crusts consisting of phosphatic coated grains. These observations confirm the importance of sulfate-reducing bacteria in the formation of the phosphatic laminite. Model calculations highlight that organic matter degradation by sulfate-reducing bacteria has the potential to liberate sufficient phosphorus for phosphogenesis.

Isotopic composition of oxygen, carbon, and sulfur in interstitial water and cores at DSDP Leg 59 Holes

Comprehensive isotopic studies based on data from the Deep Sea Drilling Project have elucidated numerous details of the low- and high-temperature mechanisms of interaction between water and rocks of ocean crustal seismic Layers 1 and 2. These isotopic studies have also identified climatic changes during the Meso-Cenozoic history of oceans. Data on the abundance and isotopic composition of sulfur in the sedimentary layer as well as in rocks of the volcanic basement are more fragmentary than are oxygen and carbon data. In this chapter we specifically concentrate upon isotopic data related to specific features of the mechanisms of low-temperature interaction of water with sedimentary and volcanogenic rocks. The Leg 59 data provide a good opportunity for such lithologic and isotopic studies, because almost 600 meters of basalt flows and sills interbedded with tuffs and volcaniclastic breccias were cored during the drilling of Hole 448A. Moreover, rocks supposedly exposed to hydrothermal alteration play an important role at the deepest horizons of that mass. Sulfur isotopic studies of the character of possible biogenic processes of sulfate reduction in sediments are another focus, as well as the nature and origin of sulfide mineralization in Layer-2 rocks of remnant island arcs. Finally, oxygen and carbon istopic analyses of biogenic carbonates in the cores also enabled us to investigate the effects of changing climatic conditions during the Cenozoic. These results are compared with previous data from adjacent regions of the Pacific Ocean. Thus this chapter describes results of isotopic analyses of: oxygen and sulfur of interstitial water; oxygen and carbon of sedimentary carbonates and of calcite intercalations and inclusions in tuffs and volcaniclastic breccias interbedded with basalt flows; and sulfur of sulfides in these rocks.

Pliocene-Pleistocene oxygen isotope record DSDP Site 586, Ontong Java Plateau, Pacific Ocean i

Oceanographic changes in the western equatorial Pacific during the past 6 Ma are inferred from oxygen isotopic analyses of planktic and benthic foraminifera from Ontong Java Plateau (DSDP Site 586). The taxa are Globigerinoides sacculifer, Pulleniatina, Cibicidoides wuellerstorfi, and Oridorsalis umbonatus. Cooling and ice buildup are indicated by an 18O enrichment of 0.3 per mil in the planktic species near 3.4 Ma. This shift apparently is compensated in the benthic data by a warming of the deep waters by between 1° and 2° C. We suggest that the dominant source of upper deep water supply to the Pacific changed from Antarctic to North Atlantic at that time, the North Atlantic-derived water being warmer. Near 2.8 Ma (approximately) the planktic foraminifera again record an enrichment in 18O (Delta delta18O=0.25 per mil). We suggest ice buildup in the northern hemisphere as the cause, because of subsequent sharp increase in fluctuations of the delta18O signal, that is, instability. The enrichment is magnified in the benthic foraminifera (Delta delta18O = 0.5 per mil) by a cooling of the deep water by 1.5° at the time, presumably signalling a glacial-type reduction of North Atlantic Deep Water (NADW) production. Episodic divergence between the signals of G. sacculifer and Pulleniatina in the Pleistocene apparently reflects periods of increased upwelling in the western equatorial Pacific. The amplitude of ice volume fluctuations cannot be reconstructed from delta18O data alone, unless there are constraints on temperature variations. The increase in amplitude of fluctuation of the benthic and planktic signals during the Pleistocene may be attributed either to an increase in maximum ice volume, or to an increase in the fractionation of continental ice, or a combination of both causes.

High-resolution in situ oxygen microprofiles, porewater and solid phase geochemistry from the Crimean shelf (Black Sea) from Maria S. Merian cruise MSM15/1

The outer western Crimean shelf of the Black Sea is a natural laboratory to investigate effects of stable oxic versus varying hypoxic conditions on seafloor biogeochemical processes and benthic community structure. Bottom-water oxygen concentrations ranged from normoxic (175 µmol O2/L) and hypoxic (< 63 µmol O2/L) or even anoxic/sulfidic conditions within a few kilometers' distance. Variations in oxygen concentrations between 160 and 10 µmol/L even occurred within hours close to the chemocline at 134 m water depth. Total oxygen uptake, including diffusive as well as fauna-mediated oxygen consumption, decreased from 15 mmol/m**2/d on average in the oxic zone, to 7 mmol/m**2/d on average in the hypoxic zone, correlating with changes in macrobenthos composition. Benthic diffusive oxygen uptake rates, comprising respiration of microorganisms and small meiofauna, were similar in oxic and hypoxic zones (on average 4.5 mmol/m**2/d), but declined to 1.3 mmol/m**2/d in bottom waters with oxygen concentrations below 20 µmol/L. Measurements and modeling of porewater profiles indicated that reoxidation of reduced compounds played only a minor role in diffusive oxygen uptake under the different oxygen conditions, leaving the major fraction to aerobic degradation of organic carbon. Remineralization efficiency decreased from nearly 100 % in the oxic zone, to 50 % in the oxic-hypoxic zone, to 10 % in the hypoxic-anoxic zone. Overall, the faunal remineralization rate was more important, but also more influenced by fluctuating oxygen concentrations, than microbial and geochemical oxidation processes.

Planktonic foraminifera oxygen isotope and trace metal data ODP Hole 172-1056A, 46-54 ka BP

Salinity increase in the subtropical gyre system may have pre-conditioned the North Atlantic Ocean for a rapid return to stronger overturning circulation and high-latitude warming following meltwater events during the Last Glacial period. Here we investigate the Gulf Stream - subtropical gyre system properties over Dansgaard-Oeschger (DO) cycles 14 to 12, including Heinrich ice-rafting event 5. During the Holocene and Last Glacial Maximum a positive gradient in surface dwelling planktonic foraminifera d18O (Globigerinoides ruber) can be observed between the Gulf Stream and subtropical gyre, due to decreasing temperature, increasing salinity, and a change from summer to year-round occurrence of G. ruber. We assess whether this gradient was a common feature during stadial-interstadial climate oscillations of Marine Isotope Stage 3, by comparing existing G. ruber d18O from ODP Site 1060 (subtropical gyre location) and new data from ODP Site 1056 (Gulf Stream location) between 54 and 46 ka. Our results suggest that this gradient was largely absent during the period studied. During the major warm DO interstadials 14 and 12 we infer a more zonal and wider Gulf Stream, influencing both ODP Sites 1056 and 1060. A Gulf Stream presence during these major interstadials is also suggested by the large vertical d18O gradient between shallow dwelling planktonic foraminifera species, especially G. ruber, and the deep dwelling species Globorotalia inflata at site 1056, which we associate with strong summer stratification and Gulf Stream presence. A major reduction in this vertical d18O gradient from 51 ka until the end of Heinrich event 5 at 48.5 ka suggests site 1056 was situated within the subtropical gyre in this mainly cold period, from which we infer a migration of the Gulf Stream to a position nearer to the continental shelf, indicative of a narrower Gulf Stream with possibly reduced transport.

Stable carbon and oxygen isotope ratios of Planulina wuellerstorfi from sediments of the Sierra Leone Rise

Causes of change in deep water delta13C can be either global or local in extent. Global causes include (1) climatically-induced changes in the amount of terrestrial biomass which alter the average carbon isotopic composition of the oceanic reservoir (Shackleton, 1977), and (2) erosion and deposition of organic-rich, continental shelf sediments during sea level fluctuations which change the mean oceanic carbon: phosphorus ratio (Broecker, 1982 doi:10.1016/0079-6611(82)90007-6). Regional gradients of delta13C are created by remineralization of organic detritus within the deep ocean itself thus reflecting the distribution of water masses and modern thermohaline flow. Changes in a single geological record of benthic foraminiferal delta13C can result from any combination of these global and abyssal circulation effects. By sampling a large number of cores collected over a wide bathymetric range yet confined to a small geographical region we have minimized the ambiguity. We can assume that each delta13C record was equally affected by global causes of delta13C variation. The differences seen between the delta13C records must, therefore, reflect changes in the distribution of delta13C in the deep ocean. We interpret these differences in distribution in terms of changes in the ocean's abyssal circulation. Benthic foraminiferal carbon isotopic evidence from a suite of Sierra Leone Rise cores indicates that the deeper parts of the eastern Atlantic basins underwent a reduction in [O2] during the maximum of the last glaciation. Reduced advection of O2-rich deep water through low-latitude fracture zones, associated with increased delivery of organic matter to the deep ocean, lowered the delta13C of deep water SumCO2 at all depths below the sill separating the eastern and western Atlantic basins (Metcalf et al., 1964 doi:10.1016/0011-7471(64)91078-2). This decreased advection into the eastern Atlantic Ocean coincides with the overall decrease in deep water production in the North Atlantic during the last glacial maximum (Curry and Lohmann, 1982 doi:10.1016/0033-5894(82)90071-0; Boyle and Keigwin, 1982 doi:10.1126/science.218.4574.784; Schnitker, 1979 doi:10.1016/0377-8398(79)90020-3; Streeter and Shackleton, 1979 doi:10.1126/science.203.4376.168).