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.

Cenozoic radiolarians from the Bahamas

Radiolarians from two sites north of Little Bahama Bank (Sites 627 and 628) are correlated with assemblages from sites on the southeastern U.S. coastal plain and continental shelf and from DSDP Sites 391 and 534 in the Blake-Bahama Basin. Results show that deposition of biogenic silica-rich sediments occurred in this region from the late Oligocene through middle Miocene, although the record is interrupted by unconformities. Radiolarians help constrain the age of a mass-transported deposit at Site 627 that appears to be coeval with the Great Abaco Member of the Blake Ridge Formation.

Chronostratigraphy of sediments from the Bahamas

Continuous cores drilled during the Bahamas Drilling Project (BDP) and the Ocean Drilling Program (ODP) Leg 166 along a transect from the top of Great Bahama Bank to the basin in the Straits of Florida provide a unique data set to test the assumption in seismic stratigraphy that seismic reflections are time lines and, thus, have a chronostratigraphic significance. Seismic reflections that are identified as seismic sequence boundaries (SSBs) were dated by means of biostratigraphy in the five ODP sites and by a combination of biostratigraphy, magnetostratigraphy and Sr isotope stratigraphy in the two BDP sites. The seismic reflection horizons are carried across a variety of facies belts from shallow-water carbonates over slope carbonates to drift deposits in the Straits of Florida. Within this system 17 SSBs were identified and dated. Despite the fact that the seismic reflections cross several facies belts, their ages remain remarkably constant. The average offset in all sites is 0.38 Myr. In no cases do the seismic reflections cut across time lines. The age differences are the combined result of the biostratigraphic sampling frequency, the spacing of marker species that required extrapolation of ages, and the resolution of the seismic data. In addition, uncertainties of age determination in the proximal sites where age-diagnostic fauna are rare add to the age differences between sites. Therefore, it can be concluded that the seismic reflections, which mark the SSBs along the Bahamas Transect, are time lines and can be used as stratigraphic markers. This finding implies that depositional surfaces are preferentially imaged by reflected seismic waves and that an impedance contrast exists across these surfaces. Facies successions across the sequence boundaries indicate that the sequence boundaries coincide with the change of deposition from times of high to low sea level. In the carbonate setting of Great Bahama Bank, sea-level changes produce changes in sediment composition, sedimentation rate and diagenesis from the platform top to the basin. The combination of these factors generates differences in sonic velocity and, thus, in impedance that cause the seismic reflection. The impedance contrasts decrease from the proximal to the distal sites, which is reflected in the seismic data by a decrease of the seismic amplitude in the basinal area.

Uranium concentrations and isotope ratios Bahamas seawater and ODP holes pore-water

The geometry, timing, and rate of fluid-flow through carbonate margins and platforms is not well constrained. In this study, we use U concentrations and isotope ratios measured on small volumes of pore-water from Bahamas slope sediment, coupled with existing chlorinity data, to place constraints on the fluid-flow in this region and, by implication, other carbonate platforms. These data also allow an assessment of the behaviour of U isotopes in an unusually well constrained water-rock system. We report pore-water U concentrations which are controlled by dissolution of high-U organic material at shallow depths in the sediment and by reduction of U to its insoluble 4+ state at greater depths. The dominant process influencing pore-water (234U/238U) is alpha recoil. In Holocene sediments, the increase of pore-water (234U/238U) due to recoil provides an estimate of the horizontal flow rate of 11 cm/year, but with considerable uncertainty. At depths in the sediment where conditions are reducing, features in the U concentration and (234U/238U) profiles are offset from one another which constrains the effective diffusivity for U in these sediments to be c. 1-2 * 10**-8 cm**2/s. At depths between the Holocene and these reducing sediments, pore-water (234U/238U) values are unusually low due to a recent increase in the dissolution rate of grain surfaces. This suggests a strengthening of fluid flow, probably due to the flooding of the banks at the last deglaciation and the re-initiation of thermally-driven venting of fluid on the bank top and accompanying recharge on the slopes. Interpretation of existing chlorinity data, in the light of this change in flow rate, constrain the recent horizontal flow rate to be 10.6 ( 3.4) cm/year. Estimates of flow rate from (234U/238U) and Cl[-] are therefore in agreement and suggest flow rates close to those predicted by thermally-driven models of fluid flow. This agreement supports the idea that flow within the Bahamas Banks is mostly thermally driven and suggests that flow rates on the order of 10 cm/year are typical for carbonate platforms where such flow occurs.

U-Th dating of marine sediments from the Bahamas slope

In order to understand the driving forces for Pleistocene climate change more fully we need to compare the timing of climate events with their possible forcing. In contrast to the last interglacial (marine isotope stage (MIS) 5) the timing of the penultimate interglacial (MIS 7) is poorly constrained. This study constrains its timing and structure by precise U-Th dating of high-resolution delta18O records from aragonite-rich Bahamian slope sediments of ODP Leg 166 (Sites 1008 and 1009). The major glacial-interglacial cycles in delta18O are distinct within these cores and some MIS 7 substages can be identified. These sediments are well suited for U-Th dating because they have uranium concentrations of up to 12 ppm and very low initial 230Th contributions with most samples showing 230Th/232Th activity ratio of >75. U and Th concentrations and isotope ratios were measured by thermal ionisation mass spectrometry and multiple collector inductively coupled plasma mass spectrometry, with the latter providing dramatically better precision. Twenty-nine of the 41 samples measured have a delta234U value close to modern seawater suggesting that they have experienced little diagenesis. Ages from 27 of the 41 samples were deemed reliable on the basis of both their U and their Th isotope ratios. Ages generally increase with depth, although we see a repeated section of stratigraphy in one core. Extrapolation of constant sedimentation rate through each substage suggests that the peak of MIS 7e lasted from ~237 to 228 ka and that 7c began at 215 ka. This timing is consistent with existing low precision radiometric dates from speleothem deposits. The beginning of both these substages appears to be slightly later than in orbitally tuned timescales. The end of MIS 7 is complex, but also appears to be somewhat later than is suggested by orbitally tuned timescales, although this event is not particularly well defined in these cores.