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.

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.

Natural gamma ray and stable isotope record of ODP Site 181-1119

Ocean Drilling Program Site 1119 is ideally located to intercept discharges of sediment from the mid-latitude glaciers of the New Zealand Southern Alps. The natural gamma ray signal from the site's sediment core contains a history of the South Island mountain ice cap since 3.9 million years ago (Ma). The younger record, to 0.37 Ma, resembles the climatic history of Antarctica as manifested by the Vostok ice core. Beyond, and back to the late Pliocene, the record may serve as a proxy for both mid-latitude and Antarctic polar plateau air temperature. The gamma ray signal, which is atmospheric, also resembles the ocean climate history represented by oxygen isotope time series.

Mineral, chemical and isotopic compositions of hydrothermally altered sediments from the Middle Valley (Juan de Fuca Ridge), ODP Site 139-858

Li and Li isotopes have been measured in the clay fraction of sediments recovered from the Middle Valley hydrothermal site on the Juan De Fuca Ridge. The Li content of pure detrital clays is 51 ppm while hydrothermal clays and carbonates have lower Li (22+/-11 ppm). However, there is no clear relationship between the mineralogy of the hydrothermal alteration products and their Li content. The d7Li value of the detrital clays is +5.8?. Hydrothermal clays and carbonates have d7Li in the range of -3.9? to +7.8?; these values do not seem to be dependent on the temperature at which they formed. Modelling of the Li and Li isotope systematics indicates that the fluid from which the alteration products form is significantly enriched in Li (higher than 10000 µmol/kg) relative to pore fluids recovered from within the sediments (up to 589 µmol/kg; [Wheat, C.G., M.J. Mottl, 1994. Data report: trace metal composition of pore water from Sites 855 through 858, Middle valley, Juan De Fuca Ridge. In Mottl, M.J., Davis, E.E., Fisher, A.T., Slack, J.F. (Eds.), Proc. ODP, Sci. Res. 139: 749-755; doi:10.2973/odp.proc.sr.139.269.1994]), and that this Li is derived from sediment. Thus, the alteration products are not in equilibrium with their conjugate pore fluids; rather, the alteration minerals formed at lower water/sediment ratios. This suggests that fluid flow pathways at Middle Valley were more diffuse in the past than they are today.

Chemistry of Globigerinoides ruber shells from ODP Site 160-963

Here we present a high-resolution faunal, floral and geochemical (stable isotopes and trace elements) record from the sediments of Ocean Drilling Program Site 963 (central Mediterranean basin), which shows centennial/millennial-scale resemblance to the high-northern latitude rapid temperature fluctuations documented in the Greenland ice cores between 20 and 70 kyr BP. Oxygen and carbon isotopes, planktic foraminifera and calcareous nannofossil distributions suggest that Dansgaard-Oeschger (D/O) and Heinrich events (HE) are distinctly expressed in the Mediterranean climate record. Moreover, recurrent though subdued oscillations not previously identified in the Lateglacial Mediterranean sediments document a significant centennial-scale climate variability in the basin that is greater than previously thought. Alternations between climate regimes dominated by polar outbreaks during D/O stadials and warm D/O interstadials, with associated intensification of continental runoff, are well expressed in the ODP Site 963. These place the Mediterranean basin as an often overlooked recorder of the interplay between large- and regional- scale climate controls at intermediate latitudes, and of the possible interactions between different components of the climate system. Significant changes in Ba/Ca values measured in Globigerinoides ruber shells from a number of D/O stadials and interstadials suggest enhanced freshwater input from the north-eastern Mediterranean borderland during the D/O interstadials. However, the short duration of 3D stratification events never led to complete oxygen consumption along the water column, but clear effects of sluggish 3D circulation in the basin are testified to by negative excursions in d13C measured in selected species of planktic and benthic foraminifera. HEs are constantly associated with lightening in the d18O record of planktic foraminifera, possibly because of the impact of iceberg melting in the Iberian Margin on Mediterranean thermohaline circulation. Interestingly, in two cases in particular, HE2 and HE5, fresher water inputs also affected deeper horizons of intermediate waters, suggesting a basin-wide impact.

Petrography, minerals and isotopic composition at DSDP Leg 66 Holes

We collected 20 carbonate nodules from the inner trench slope deposits of the Middle America Trench area off Mexico. Carbonate nodules are found only within the methane-rich layer beneath the mixed layer of methane and hydrogen sulfide. They have been investigated by microscopic, scanning electron microscopic (SEM), X-ray diffraction, and stable isotopic analytical methods. Calcite, magnesian calcite, dolomite, and rhodochrosite were recognized as carbonate minerals. Each carbonate nodule is usually represented by single species of carbonate minerals. Carbonate nodules are subdivided into micrite nodules and recrystallized nodules according to textural features. The carbonate crystallites in each micrite nodule are equidimensional. Their sizes range from several to 30 µm, as revealed by SEM micrographs. The chemical composition of calcite is changed from pure calcite to high magnesian calcite, as shown by the shift of the (104) reflection in X-ray diffraction patterns. Fe substitution for Ca in dolomite was also observed. Carbon isotopic composition shows an unusually wide range - from -42.9 to +13.5 per mil - in PDB scale, whereas oxygen isotopic compositions of almost all the carbonate nodules are constantly enriched in 18O from +3.4 to +7.60 per mil in PDB scale. These wide variations in carbon isotopic composition indicate several sources for the carbon in carbonate nodules. Carbon with a negative d13C value was derived from biochemical oxidation of methane with a negative d13C value. On the other hand, carbon with positive d13C value was probably formed during methane production in an anoxic condition.