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.

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.