Inorganic geochemistry, epoch and water content in sediments at DSDP Site 91-596

Originally, we had planned to piston core at Site 595 in order to meet the sedimentologic and biostratigraphic objectives outlined in the introductory chapter. However, consultation with our colleagues, Thomas Jordan and John Orcutt on board Melville, indicated that coring near the ocean bottom seismometer (OBS) array around Hole 595B could alter the programmed signal to noise ratio above which teleseisms trigger recording in the OBSs. They requested that we core no closer than about 8 km from three OBSs nearest Hole 595B, and selected a target for us about that distance to the west. Since a new beacon was required at this distance, a new site number, 596, was designated. Briefly, we planned to obtain oriented hydraulic piston cores to the top of the cherts, then core through the cherts using the extended core barrel (XCB) to basement. With improved recovery, we hoped to reach the sediment/basalt contact, and thus obtain a reliable biostratigraphic determination of the basement age. We planned to obtain at least one core in basement, perhaps more, with time permitting. We planned no geophysical program for the hole.

Geochemistry and morphometry on planktonic foraminifera

About one third of the anthropogenic carbon dioxide (CO2) released into the atmosphere in the past two centuries has been taken up by the ocean. As CO2 invades the surface ocean, carbonate ion concentrations and pH are lowered. Laboratory studies indicate that this reduces the calcification rates of marine calcifying organisms, including planktic foraminifera. Such a reduction in calcification resulting from anthropogenic CO2 emissions has not been observed, or quantified in the field yet. Here we present the findings of a study in the Western Arabian Sea that uses shells of the surface water dwelling planktic foraminifer Globigerinoides ruber in order to test the hypothesis that anthropogenically induced acidification has reduced shell calcification of this species. We found that light, thin-walled shells from the surface sediment are younger (based on 14C and d13C measurements) than the heavier, thicker-walled shells. Shells in the upper, bioturbated, sediment layer were significantly lighter compared to shells found below this layer. These observations are consistent with a scenario where anthropogenically induced ocean acidification reduced the rate at which foraminifera calcify, resulting in lighter shells. On the other hand, we show that seasonal upwelling in the area also influences their calcification and the stable isotope (d13C and d18O) signatures recorded by the foraminifera shells. Plankton tow and sediment trap data show that lighter shells were produced during upwelling and heavier ones during non-upwelling periods. Seasonality alone, however, cannot explain the 14C results, or the increase in shell weight below the bioturbated sediment layer. We therefore must conclude that probably both the processes of acidification and seasonal upwelling are responsible for the presence of light shells in the top of the sediment and the age difference between thick and thin specimens.

Geochemistry of interstitial gases in sedimentary deposits at DSDP Leg 64 Holes

We analyzed interstitial gases from holes at Sites 474, 477, 478, 479, and 481 in the Gulf of California, using gas chromatography and stable isotope mass spectrometry to evaluate their composition in terms of biogenic and thermogenic sources. The hydrocarbon gas (C1-C5) concentrations were comparable to the shipboard data, and no olefins could be detected. The ?13C data for the CH4 confirmed the effects of thermal stress on the sedimentary organic matter, because the values were typically biogenic near the surface and became more depleted in 12C versus depth in holes at Sites 474, 478, and 481. The CH4 at Site 477 was the heaviest, and in Hole 479 it did not show a dominant hightemperature component. The CO2 at depth in most holes was mostly thermogenic and derived from carbonates. The low concentrations of C2-C5 hydrocarbons in the headspace gas of canned sediments precluded a stable carbon-isotope analysis of their genetic origin.

Geochemistry and radiolarian distribution of sediment core MD96-2073

A combination of changes in the species composition of the radiolarian populations, and in the sediment chemical composition (content and mass accumulation rates of carbonate, organic carbon, and selected major and trace elements, with special attention paid to Ba) is used to reconstruct the variations in upwelling activity over the last 250 kyr in the Socotra gyre area (Somali-Socotra upwelling system, NW Indian Ocean). In the Socotra gyre (Core MD 962073 at 10°N), the variations in upwelling intensity are reconstructed by the upwelling radiolarian index (URI) while the thermocline/surface radiolarian index (TSRI) testifies to productivity variations during non-upwelling intervals. Despite an origin related both to marine and terrigenous inputs, the geochemical records of organic carbon, silica, and trace elements (Ba, P, Cu, and Zn) normalized to Al are controlled by the variations in surface paleoproductivity. The data indicate a continuous increase in upwelling intensity during the last 250 kyr with a maximum activity within the MIS 3, while high productivity periods in between the upwelling seasons occurred both during glacial and interglacial intervals. A comparison of our data with published observations from another gyre of the Somalian upwelling area located at 5°N in the Somali gyre area shows differences regarding periods of upwelling activity and their geochemical imprint. Three hypotheses are proposed to explain these differences: (1) changes in the planktonic community, resulting in more silica-rich deposits in the Socotra gyre, and more carbonate-rich deposits in the Somali gyre, that are controlled by differences in the source water of the upwelling; (2) a more important terrigenous input in the southern gyre; and (3) a different location of the sites relative to the geographic distribution of the upwelling gyres and hydrologic fronts.

Geochemistry on manganese nodules from Timor

Fossil Mn nodules of Cretaceous age from western Timor exhibit chemical, structural and radioisotope compositions consistent with their being of deep-sea origin. These nodules show characteristics similar to nodules now found at depths of 3,500-5,000 m in the Pacific and Indian Oceans. Slight differences in the fine structure and chemistry of these nodules and modern deep-sea nodules are attributed to diagenetic alteration after uplift of enclosing sediments.

Rare earth and other element contents in surface layer bottom sediments and ferromanganese nodules along the Transatlantic profile

Behavior of rare earth elements (REE) and Th is studied along the Transatlantic transect at 22°N. It is shown that both REE and Th contents relative to Al (the most lithogenic element) increase toward the pelagic region. The increasing trend becomes more complicated due to variations in content of biogenic calcium carbonate that acts as a diluting component in sediments. REE composition varies symmetrically relative to the Mid-Atlantic Ridge (MAR) emphasizing weak hydrothermal influence on sediments of the ridge axis, although the well-known criteria for hydrothermal contribution, such as Al/(Al+Mn+Fe) and (Fe+Mn)/Ti, do not reach critical values. Variations in REE content and composition allowed to distinguish the following five sediment zones in the transect: (I) terrigenous sediments of the Nares abyssal plain; (II) pelagic sediments of the North American Basin; (III) carbonate ooze of the MAR axis; (IV) pelagic sediments of the Canary Basin; and (V) terrigenous clay and calcareous mud of the African continental slope and slope base. Ferromanganese nodules of the hydrogenous type with extremely high Ce (up to 1801 ppm) and Th (up to 138 ppm) contents occur in pelagic sediments. It is ascertained that P, REE, and Th contents depend on Fe content in Atlantic sediments. Therefore, one can suggest that only minor amount of phosphorus is bound with bone debris. Low concentration of bone debris phosphorus is a result of relatively high sedimentation rates in the Atlantic Ocean, as compared with those in pelagic regions of the Pacific Ocean.

Composition of surface layer bottom sediments from the Chukchi Sea

Abundance of noble metals and bulk chemical composition have been studied in bottom sediments of the Chukchi Sea. Distribution of noble metals and their correlation with major and trace elements in the sediments have been analyzed using multicomponent statistics. It was established that average contents of noble metals in the bottom sediments of the Chukchi Sea significantly exceed those both in shelf terrigenous sediments and stratisphere. Osmium and iridium enrich mixed and pelitic sediments relative to shallow-water sediments and their influx is presumably determined by erosion of coastal and bottom unconsolidated deposits. High Ag, Ru, Au, and Pt contents were identified in clayey sediments enriched in biogenic elements in the some areas of the Southern Chukchi plain (Chukchi Sea) confined to intersection zones of submeridional and sublatitudinal structures of the graben-rift system, which formed in Mesozoic and activated in Late Cenozoic.

Geochemistry of planktonic foraminifera of sediment core MD97-2121

In situ measurements of Mg/Ca, Zn/Ca, Mn/Ca, and Ba/Ca in Globigerinoides bulloides and Globigerina ruber from southwest Pacific core top sites and plankton tow are reported and their potential as paleoproxies is explored. The modern samples cover 20° of latitude from 34°S to 54°S, 7-19°C water temperature, and variable influence of subantarctic (SAW) and subtropical (STW) surface waters. Trace element signatures recorded in core top and plankton tow planktic foraminifera are examined in the context of the chemistry and nutrient profiles of their modern water masses. Our observations suggest that Zn/Ca and Mn/Ca may have the potential to trace SAW and STW. Intraspecies and interspecies offsets identified by in situ measurements of Mg/Ca and Zn/Ca indicate that these ratios may also record changes in thermal and nutrient stratification in the upper ocean. We apply these potential proxies to fossilized foraminifera from the high-resolution core MD97 2121. At the Last Glacial Maximum, surface water Mg/Ca temperature estimates indicate that temperatures were approximately 6-7°C lower than those of the present, accompanied by low levels of Mn/Ca and Zn/Ca and minimal thermal and nutrient stratification. This is consistent with regional dominance of SAW and reduced STW inflow associated with a reduced South Pacific Gyre (SPG). Upper ocean thermal and nutrient stratification collapsed during the Antarctic Cold Reversal, before poleward migration of the zonal winds and ocean fronts invigorated the SPG and increased STW inflow in the early Holocene. Together with reduced winds, this favored a stratified upper ocean from circa 10 ka to the present.

Geochemistry and mineralogy of sediments from the Atlantis II Fracture Zone

Thirteen sediment samples, including calcareous ooze, sandy clay, volcanic sand, gravel, and volcanic breccia, from Ocean Drilling Program (ODP) Sites 732B, 734B, 734G and Conrad Cruise 27-9, Station 17, were examined. Contents of major and trace elements were determined using XRF or ICP (on samples <0.5 g). Determinations of rare earth elements (REE) were performed using ICP-MS. Mineralogy was determined using XRD. On the basis of the samples studied, the sediments accumulating in the Atlantis II Fracture Zone are characterized by generally high MgO, Cr, and Ni contents compared with other deep-sea sediments. A variety of sources are reflected in the mineralogy and geochemistry of these sediments. Serpentine, brucite, magnetite, and high MgO, Cr, and Ni contents indicate derivation from ultramafic basement. The occurrence of albite, analcime, primary mafic minerals, and smectite/chlorite in some samples, coupled with high SiO2, Al2O3, TiO2, Fe2O3, V, and Y indicate contribution from basaltic basement. A third major sediment source is characterized as biogenic material and is reflected primarily in the presence of carbonate minerals, and high CaO, Sr, Pb, and Zn in certain samples. Kaolinite, illite, quartz, and some chlorite are most likely derived from continental areas or other parts of the ocean by long-distance sediment transport in surface or other ocean currents. Proportions of source materials in the sediments reflect the thickness of the sediment cover, slope of the seafloor, and the nature of and proximity to basement lithologies. REE values are low compared to other deep-sea sediments and indicate no evidence of hydrothermal activity in the Atlantis II Fracture Zone sediments. This is supported by major- and trace-element data.

Geochemistry of sediment cores from METEOR cruise M76/1b

Marine sediments are the main sink in the oceanic phosphorus (P) cycle. The activity of benthic microorganisms is decisive for regeneration, reflux, or burial of inorganic phosphate (Pi), which has a strong impact on marine productivity. Recent formation of phosphorites on the continental shelf and a succession of different sedimentary environments make the Benguela upwelling system a prime region for studying the role of microbes in P biogeochemistry. The oxygen isotope signature of pore water phosphate (d18OP) carries characteristic information of microbial P cycling: Intracellular turnover of phosphorylated biomolecules results in isotopic equilibrium with ambient water, while enzymatic regeneration of Pi from organic matter produces distinct offsets from equilibrium. The balance of these two processes is the major control for d18OP. Our study assesses the importance of microbial P cycling relative to regeneration of Pi from organic matter from a transect across the Namibian continental shelf and slope by combining pore water chemistry (sulfate, sulfide, ferrous iron, Pi), steady-state turnover rate modeling, and oxygen isotope geochemistry of Pi. We found d18OP values in a range from 12.8 per mill to 26.6 per mill, both in equilibrium as well as pronounced disequilibrium with water. Our data show a trend towards regeneration signatures (disequilibrium) under low mineralization activity and low Pi concentrations, and microbial turnover signatures (equilibrium) under high mineralization activity and high Pi concentrations. These findings are opposite to observations from water column studies where regeneration signatures were found to coincide with high mineralization activity and high Pi concentrations. It appears that preferential Pi regeneration in marine sediments does not necessarily coincide with a disequilibrium d18OP signature. We propose that microbial Pi uptake strategies, which are controlled by Pi availability, are decisive for the alteration of the isotope signature. This hypothesis is supported by the observation of efficient microbial Pi turnover (equilibrium signatures) in the phosphogenic sediments of the Benguela upwelling system.

(Tabls S1) Bulk geochemistry for sediment samples collected from the Cenomanian-Turonian boundary section at Pont d'Issole

Oceanic Anoxic Event 2 (OAE2), spanning the Cenomanian-Turonian boundary (CTB), represents one of the largest perturbations in the global carbon cycle in the last 100 Myr. The d13Ccarb, d13Corg, and d18O chemostratigraphy of a black shale-bearing CTB succession in the Vocontian Basin of France is described and correlated at high resolution to the European CTB reference section at Eastbourne, England, and to successions in Germany, the equatorial and midlatitude proto-North Atlantic, and the U.S. Western Interior Seaway (WIS). Delta13C (offset between d13Ccarb and d13Corg) is shown to be a good pCO2 proxy that is consistent with pCO2 records obtained using biomarker d13C data from Atlantic black shales and leaf stomata data from WIS sections. Boreal chalk d18O records show sea surface temperature (SST) changes that closely follow the Delta13C pCO2 proxy and confirm TEX86 results from deep ocean sites. Rising pCO2 and SST during the Late Cenomanian is attributed to volcanic degassing; pCO2 and SST maxima occurred at the onset of black shale deposition, followed by falling pCO2 and cooling due to carbon sequestration by marine organic productivity and preservation, and increased silicate weathering. A marked pCO2 minimum (~25% fall) occurred with a SST minimum (Plenus Cold Event) showing >4°C of cooling in ~40 kyr. Renewed increases in pCO2, SST, and d13C during latest Cenomanian black shale deposition suggest that a continuing volcanogenic CO2 flux overrode further drawdown effects. Maximum pCO2 and SST followed the end of OAE2, associated with a falling nutrient supply during the Early Turonian eustatic highstand.

Organic geochemistry records from two Palaeocene-Eocene Thermal Maximum sections in Denmark

Analysis of sediments deposited at different latitudes around the world during the Palaeocene-Eocene Thermal Maximum (PETM; ~56 Ma) have revealed a globally profound warming phase, regionally varying from 5-8 °C. Such records from Europe have not yet been obtained. We studied the variations in sea surface and continental mean annual air temperatures (SST and MAT, respectively) and the distribution patterns and stable carbon isotopes of higher plant derived n-alkanes in two proximal PETM sections (Fur and Store Bælt, Denmark) from the epicontinental North Sea Basin. A negative carbon isotope excursion (CIE) of 4-7 per mil was recorded in land plant derived n-alkanes, similar to what has been observed for other PETM sections. However, differences observed between the two proximal sites suggest that local factors, such as regional vegetation and precipitation patterns, also influenced the CIE. The presence of S-bound isorenieratene derivatives at the onset of the PETM and increased organic carbon contents points to a rapid shift in depositional environment; from well oxygenated to anoxic and sulfidic. These euxinic conditions are comparable with those during the PETM in the Arctic Ocean. SSTs inferred from TEX86 show relatively low temperatures followed by an increase of ~7 °C across the PETM. At the Fur section, a remarkably similar temperature record was obtained for MAT using the MBT'/CBT proxy. However, the MAT record of the Store Bælt section did not reveal this warming.

Mineralogy and geochemistry of aerosols from the Western Pacific

Aerosols collected by net method over the Western Pacific were investigated. Distribution of eolian material, its mineral and chemical compositions are controlled by the climatic and circumcontinental zonalities. It was stated that Fe and Mn were bound with mineral components of aerosols, while trace elements are bound with organogenic matter. Fluxes of aerosols and their components on the ocean surface were determined.