Geochemistry and sea-surface temperature reconstruction for sediment cores of the Iberian Margin

Biogenic records of the marine palaeoproductivity (carbonates, organic carbon, and C37 alkenones) and the molecular stratigraphy of past sea surface temperatures (SSTs; UK'37) were studied at high resolution in two cores of the Iberian Margin. The comparison of these records indicates that the oceanographic conditions switched abruptly during the past 160 kyr between three kinds of regimes. A first regime with high (17-22°C) SST and low productivity typifies the interglacial periods, marine isotopic stages (MIS) 5 and 1. Several periods during MIS 6, 2, and the terminations II and I are characterised by about 4-5°C colder SST and a higher organic matter accumulation, both of which define the second regime. This anticorrelation between SST and marine productivity suggests that these variations are related to the intensity of the coastal upwelling. By contrast with this upwelling behaviour, extremely low biological productivity and very cold SST (6-12°C) occurred during short phases of glacial MIS 6, 4, and 2, and as abrupt events (~1 kyr or less) during MIS 3. The three oceanographic regimes are consistent with micropalaeontological changes in the same cores based on foraminifera and diatoms. The general trend of these hydrologic changes follows the long-term glacial/interglacial cycle, but the millennium scale variability is clearly related to Heinrich events and Dansgaard-Oeschger cycles. Strengthening of the upwelling corresponds probably to an intensification of the subtropical atmospheric circulation over the North Atlantic which was influenced by the presence of continental ice sheets. However, extreme glacial conditions due to massive discharges of icebergs interrupted the upwelling. Interestingly, both terminations II and I coincided with strong but transient intensification of the upwelling.

Exchange capacity and chemical composition of Fe-Mn nodules from the Central Pacific

Constants of calcium, magnesium, zinc, cobalt, copper, and nickel exchange for sodium in iron-manganese nodules taken from different parts of the Pacific Ocean were determined under static conditions at constant ionic strength (?=0.05). These determinations revealed high capacity of nodules for sorbing the referred ions (their exchange constants range from 1.93 to 20.85). Obtained data demonstrate the major role of MnO and Fe2O3 in sorption processes in iron-manganese nodules.

Composition of sedimentary rocks from the Mountainous Crimea and the Northwestern Caucasus

Detailed data obtained on chemistry of sedimentary rocks from the Mountainous Crimea and the Northwestern Caucasus that were dated at the Cenomanian/Turonian boundary and formed during Oceanic Anoxic Event 2 make it possible to calculate dissolved oxygen concentration in bottom waters of the sedimentation basin. Enrichment factors of trace elements in black shales are revised and an explanation is suggested for genesis of the rocks with regard for unusual climatic changes.

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.

Structural group composition of low-polarity organic matter dissolved in waters of the Northwest Indian Ocean and the Red Sea

Data on amounts of various functional groups, i.e. aldehyde, acid, ester, alcohol, thiol and aromatic groups in several fractions of low-polarity dissolved organic matter are presented. An assumption that this organic matter is part of the lipid fraction is not confirmed. Amount of aromatic compounds in waters of the Northwest Indian Ocean is estimated to be about 1000 times higher than quantity of aromatic hydrocarbons discharged into the ocean each year in petroleum and petroleum products.

Chemistry of interstitial waters and sediments at DSDP Leg 64 Holes

Studies of interstitial waters obtained from DSDP Leg 64 drill sites in the Gulf of California have revealed information both on early diagenetic processes in the sediments resulting from the breakdown of organic matter and on hydrothermal interactions between sediments and hot doleritic sill intrusions into the sediments. In all the sites drilled sulfate reduction occurred as a result of rapid sediment accumulation rates and of relatively high organic carbon contents; in most sites methane production occurred after sulfate depletion. Associated with this methane production are high values of alkalinity and high concentrations of dissolved ammonia, which causes ion exchange processes with the solid phases leading to intermediate maxima in Mg++, K+, Rb+, and Sr++(?). Though this phenomenon is common in Leg 64 drill sites, these concentration reversals had been noticed previously only in Site 262 (Timor Trough) and Site 440 (Japan Trench). Penetrating, hot dolerite sills have led to substantial hydrothermal alteration in sediments at sites drilled in the Guaymas Basin. Site 477 is an active hydrothermal system in which the pore-water chemistry typically shows depletions in sulfate and magnesium and large increases in lithium, potassium, rubidium, calcium, strontium, and chloride. Strontium isotope data also indicate large contributions of volcanic matter and basalt to the pore-water strontium concentrations. At Sites 478 and 481 dolerite sill intrusions have cooled to ambient temperatures but interstitial water concentrations of Li+, Rb+, Sr++ , and Cl- show the gradual decay of a hydrothermal signal that must have been similar to the interstitial water chemistry at Site 477 at the time of sill intrusion. Studies of oxygen isotopes of the interstitial waters at Site 481 indicate positive values of d18O (SMOW) as a result of high-temperature alteration reactions occurring in the sills and the surrounding sediments. A minimum in dissolved chloride at about 100-125 meters sub-bottom at Sites 478, 481, and particularly Site 479 records a possible paleosalinity signal, associated with an event that substantially lowered salinities in the inner parts of the Gulf of California during Quaternary time.

Interstitial water chemistry at DSDP Leg 67 Holes

Interstitial water chemistry has proved to be a sensitive indicator for early diagenetic reactions, particularly those related to organic matter oxidation. Downhole chemical variations in the pore waters from Deep Sea Drilling Project Holes 496 and 497 on the Middle America Trench slope off Guatemala are anomalous because both salinity and chlorinity show strong decreases to half the values of seawater, and d18O values become positive (maximum of about +2.5% at the bottom of the holes). These observations are explained in terms of dilution of pore waters after retrieval as a result of decomposition of the gas hydrates before removal of pore waters by shipboard squeezing techniques. In all holes, except Hole 495 (drilled in pelagic sediments), decomposition of organic matter leads to rapid sulfate depletion and subsequent methane generation. Associated with methane generation are large increases in alkalinity and dissolved ammonia. The latter component causes ion exchange reactions with clay minerals, which results in maxima in magnesium and perhaps potassium. At greater depths, as yet unidentified reactions cause the removal of magnesium. Especially in the deeper Trench Sites 499 and 500, rapid variations in calcium, magnesium, and alkalinity occur in turbidite sequences.

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.