Carbon and nitrogen isotopic composition of Early Toarcian sediments

Bulk sedimentary nitrogen isotope (d15Ntot) data have been generated from Lower Jurassic black, carbon-rich shales in the British Isles and northern Italy deposited during the early Toarcian oceanic anoxic event. A pronounced positive d15Ntot excursion through the exaratum Subzone of the falciferum Zone (defined by characteristic ammonites in the British Isles) broadly correlates with a relative maximum in weight percent total organic carbon and, in some sections, with a negative d13Corg excursion. Upwelling of a deoxygenated water mass that had undergone partial denitrification is the likely explanation for relative enrichment of d15Ntot, and parallels may be drawn with Quaternary sediments of the Arabian Sea, Gulf of California, and northwest Mexican margin. The development of Early Toarcian suboxic water masses and consequent partial denitrification is attributed to increases in organic productivity. Approximately coincident phenomena include the following: a relative climatic optimum, realignment of major oceanic current systems, and a possible release of methane gas hydrates from continental margin sediments early in the history of the oceanic anoxic event.

Calcareous nannofossil stratigraphy, nannofossil events and carbon isotopic ratios of ODP Leg 183 sites

Cores from Sites 1135, 1136, and 1138 of Ocean Drilling Program Leg 183 to the Kerguelen Plateau (KP) provide the most complete Paleocene and Eocene sections yet recovered from the southern Indian Ocean. These nannofossil-foraminifer oozes and chalks provide an opportunity to study southern high-latitude biostratigraphic and paleoceanographic events, which is the primary subject of this paper. In addition, a stable isotope profile was established across the Cretaceous/Tertiary (K/T) boundary at Site 1138. An apparently complete K/T boundary was recovered at Site 1138 in terms of assemblage succession, isotopic signature, and reworking of older (Cretaceous) nannofossil taxa. There is a significant color change, a negative carbon isotope shift, and nannofossil turnover. The placement of the boundary based on these criteria, however, is not in agreement with the available shipboard paleomagnetic stratigraphy. We await shore-based paleomagnetic study to confirm or deny those preliminary results. The Paleocene nannofossil assemblage is, in general, characteristic of the high latitudes with abundant Chiasmolithus, Prinsius, and Toweius. Placed in context with other Southern Ocean sites, the biogeography of Hornibrookina indicates the presence of some type of water mass boundary over the KP during the earliest Paleocene. This boundary disappeared by the late Paleocene, however, when there was an influx of warm-water discoasters, sphenoliths, and fasciculiths. This not only indicates that during much of the late Paleocene water temperatures were relatively equable, but preliminary floral and stable isotope analyses also indicate that a relatively complete record of the late Paleocene Thermal Maximum event was recovered at Site 1135. It was only at the beginning of the middle Eocene that water temperatures began to decline and the nannofossil assemblage became dominated by cool-water species while discoaster and sphenolith abundances and diversity were dramatically reduced. One new taxonomic combination is proposed, Heliolithus robustus Arney, Ladner, and Wise.

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.

Temporal evolution of organic carbon and lipid content and derived SST of sediment core GIK23258-2, Norwegian Sea

Lipids are used for the evaluation of the different organic matter contributions in the north eastern Norwegian sea (M23258 site; 75ºN, 14ºE) over the last 15,000 years. Development of a mass balance model based on the down core quantification of the C37 alkenones, the odd carbon numbered n-alkanes (Aodd) and the unresolved complex mixture of hydrocarbons (UCM) has allowed three main organic matter inputs involving marine, continental and ancient reworked organic matter to be recognized. The model shows a good agreement between measured and reconstructed TOC values. Similarly, a strong parallelism is observed between predicted components such as marine TOC and carbonate content (CaCO3), which was determined independently. Representation of the model results within a time-scale based on 15 AMS-14C measurements shows that the main changes in organic matter constituents are coincident with the major climatic events of the last 15,000 a. Thus, the predominance of reworked organic matter is characteristic of Termination Ia (up to 70%), continental organic matter was dominant during the Bølling-Allerød (B-A) and Younger Dryas (YD) periods (about 85%) and a strong increase of marine organic matter occurred in the Holocene (between 50 and 75%). This agreement reflects the main hydrographic changes that determined the deposition of sedimentary materials during the period studied: ice-rafted detritus from the Barents continental platform, ice-melting waters from the Arctic fluvial system discharging into the Barents sea and dominance of north Atlantic currents, respectively. In this respect, the high-resolution down core record resulting from the mass balance and lipid measurements allows the identification of millennial-scale events such as the increase of reworked organic matter at the final retreat of the Barents ice sheet at the end of the deglaciation period (Termination Ib).

Measurements of trace metal abundances and isotopes in carbonate sediments, Exuma, Bahamas

In order to validate the use of 238U/235U as a paleoredox proxy in carbonates, we examined the incorporation and early diagenetic evolution of U isotopes in shallow Bahamian carbonate sediments. Our sample set consists of a variety of primary precipitates that represent a range of carbonate producing organisms and components that were important in the past (scleractinian corals, calcareous green and red algae, ooids, and mollusks). In addition, four short push cores were taken in different depositional environments to assess the impact of early diagenesis and pore water chemistry on the U isotopic composition of bulk carbonates. We find that U concentrations are much higher in bulk carbonate sediments (avg. 4.1 ppm) than in primary precipitates (avg. 1.5 ppm). In almost all cases, the lowest bulk sediment U concentrations were as high as or higher than the highest concentrations found in primary precipitates. This is consistent with authigenic accumulation of reduced U(IV) during early diagenesis. The extent of this process appears sensitive to pore water H2S, and thus indirectly to organic matter content. d238/235U values were very close to seawater values in all of the primary precipitates, suggesting that these carbonate components could be used to reconstruct changes in seawater U geochemistry. However, d238/235U of bulk sediments from the push cores was 0.2-0.4 per mil heavier than seawater (and primary precipitates). These results indicate that authigenic accumulation of U under open-system sulfidic pore water conditions commonly found in carbonate sediments strongly affects the bulk U concentrations and 238U/235U ratios. We also report the occurrence of dolomite in a tidal pond core which contains low 234U/238U and 238U/235U ratios and discuss the possibility that the dolomitization process may result in sediments depleted in 238U. From this initial exploration, it is clear that 238U/235U variations in ancient carbonate sediments could be driven by changes in global average seawater, by spatial and temporal variations in the local deposition environment, or subsequent diagenesis. To cope with such effects, proxies for syndepositional pore water redox conditions (e.g., organic matter content, iron speciation, and trace metal distributions) and careful consideration of possible post-deposition alteration will be required to avoid spurious interpretation of 238U/235U data from ancient carbonate sediments.

Sea surafce temperature reconstruction for sediment core SU81-18

Reconstructing the impact of Heinrich events outside the main belt of ice rafting is crucial to understanding the underlying causes of these abrupt climatic events. A high-resolution study of a marine sediment core from the Iberian margin demonstrates that this midlatitude area was strongly affected both by cooling and advection of low-salinity arctic water masses during the last three Heinrich events. These paleoclimatic time series reveal the internal complexity of each of the last three Heinrich events and illustrate the value of parallel studies of the organic and inorganic fractions of the sediments.

Stable isotope ratios of foraminifera from the continental shelf off Troms, Northern Norway

A stable oxygen and carbon isotope stratigraphy is established for a Late Weichselian/Holocene glaciomarine/marine seguence in Andfjorden and Malangsdjupet on the continental shelf off Troms, Northern Norway. The stratigraphy demonstrates that the global signals, Termination I B and possibly also I A (upper parts), are present and radiocarbon date to 10.3-9.7 kyr B.P. and >14-13.5 kyr B.P., respectively. A temperature increase of 5°-6°C and possibly a small salinity increase occurred during Term. I. A near-glacial environment between 13 and 14 kyr B.P. was characterized by poorly ventilated bottom waters followed by a meltwater pulse at circa 13 kyr B.P. During the beginning intrusion of Atlantic Water between 13 and 10 kyr B.P., the bottom water was characterized by somewhat fluctuating temperatures and salinities. Temperatures close to those of the present were established around 9.7 kyr B.P. and seem to have been rather stable since.

Mineralogical and isotopic compositions of ODP Hole 107-650A

Red-brown dolomitic claystones overlay the Marsili Basin basaltic basement at ODP Site 650. Sequential leaching experiments reveal that most of the elements considered to have a hydrothermal or hydrogenous origin in a marine environment, such as Fe, Cu, Zn, Pb, Co, Ni, are present mainly in the aluminosilicate fraction of the dolomitic claystones. Their vertical distribution, content and partitioning chemistry of trace elements, and REE patterns suggest enhanced terrigenous input during dolomite formation, but no significant hydrothermal influence from the underlying basaltic basement. Positive correlations in the C and O isotopes in the dolomites reflect complex conditions during the dolomitization. The stable isotopes can be controlled in part by temperature variations during the dolomitization. Majority of the samples, however, form a trend that is steeper than expected for only temperature control on the C and O isotopes. The latter indicates possible isotopic heterogeneity in the proto-carbonate that can be related to arid climatic conditions during the formation of the basal dolomitic claystones. In addition, the dolostones stable isotopic characteristics can be influenced by diagenetic release of heavier delta18O from clay dehydration and/or alteration of siliciclastic material. Strontium and Pb isotopic data reveal that the non-carbonate fraction, the "dye" of the dolomitic claystones, is controlled by Saharan dust (75%-80%) and by material with isotopic characteristics similar to the Aeolian Arc volcanoes (20%-25%). The non-carbonate fraction of the calcareous ooze overlying the dolomitic claystones has a Sr and Pb isotopic composition identical to that of the dolomitic claystones, indicating that no change in the input sources to the sedimentary basin occurred during and after the dolomitization event. Combination of climato-tectonic factors most probably resulted in suitable conditions for dolomitization in the Marsili and the nearby Vavilov Basins. The basal dolomitic claystone sequence was formed at the initiation of the opening of the Marsili Basin (~2 Ma), which coincided with the consecutive glacial stage. The glaciation caused arid climate and enhanced evaporation that possibly contributed to the stable isotope variations in the proto-carbonate. The conductive cooling of the young lithosphere produced high heat flow in the region, causing low-temperature passive convection of pore waters in the basal calcareous sediment. We suggest that this pumping process was the major dolomitization mechanism since it is capable of driving large volumes of seawater (the source of Mg2+) through the sediment. The red-brown hue of the dolomitic claystones is terrigenous contribution of the glacially induced high eolian influx and was not hydrothermally derived from the underlying basaltic basement. The detailed geochemical investigation of the basal dolomitic sequence indicates that the dolomitization was most probably related to complex tectono-climatic conditions set by the initial opening stages of the Marsili Basin and glaciation.