U and Th concentrations and isotope ratios of samples from ODP Leg 166

Constraining the history of seawater (234U/238U) is important because this ratio is used to assess the validity of U/Th ages, and because it provides information about the past rate of physical weathering on the continents. This study makes use of U-rich slope sediments from the Bahamas in an attempt to reconstruct seawater (234U/238U) for the last 800 kyr. For the last 360 kyr, U/Th dating of these sediments provides ages and initial (234U/238U) values. Sixty-seven samples, largely from marine highstands, have initial (234U/238U) which scatter somewhat about the modern seawater value (~1.145) but neither this scatter nor the average value increases with age of sample. These data contrast with published coral data and suggest that seawater (234U/238U) has remained within 15? of the modern value for the last 360 kyr. This confirms the rejection of coral U/Th ages where the initial (234U/238U) is significantly different from modern seawater. Data from older highstands, dated with delta18O stratigraphy or by the presence of the Brunhes/Matuyama (B/M) reversal at 780 kyr, allow seawater (234U/238U) to be assessed prior to the range of the 230Th chronometer. Unfortunately, diagenetic scatter in the data between the B/M reversal and 360 kyr is rather large, probably relating to low U concentrations for these samples. But there is no indication of a trend in seawater (234U/238U) with age. High U samples from close to the B/M reversal show less diagenetic scatter and an initial (234U/238U) that averages 1.102. This lower value can be explained by lower seawater (234U/238U) at the time of the B/M reversal, or by progressive loss of 234U from the sediment by alpha-recoil. A simple box model is presented to illustrate the response of seawater (234U/238U) to variations in riverine input, such as might be caused by changes in continental weathering. Comparison of the Bahamas (234U/238U) data with model results indicates that riverine (234U/238U) has not varied by more than 65? for any 100 kyr period during the last 360 kyr. It also indicates that the ratio of physical to chemical weathering on the continents has not been higher than at present for any extended period during the last 800 kyr.

Geochemistry of ODP Site 145-882

Measurements of benthic foraminiferal cadmium:calcium (Cd/Ca) have indicated that the glacial-interglacial change in deep North Pacific phosphate (PO4) concentration was minimal, which has been taken by some workers as a sign that the biological pump did not store more carbon in the deep glacial ocean. Here we present sedimentary redox-sensitive trace metal records from Ocean Drilling Program (ODP) Site 882 (NW subarctic Pacific, water depth 3244 m) to make inferences about changes in deep North Pacific oxygenation - and thus respired carbon storage - over the past 150,000 yr. These observations are complemented with biogenic barium and opal measurements as indicators for past organic carbon export to separate the influences of deep-water oxygen concentration and sedimentary organic carbon respiration on the redox state of the sediment. Our results suggest that the deep subarctic Pacific water mass was depleted in oxygen during glacial maxima, though it was not anoxic. We reconcile our results with the existing benthic foraminiferal Cd/Ca by invoking a decrease in the fraction of the deep ocean nutrient inventory that was preformed, rather than remineralized. This change would have corresponded to an increase in the deep Pacific storage of respired carbon, which would have lowered atmospheric carbon dioxide (CO2) by sequestering CO2 away from the atmosphere and by increasing ocean alkalinity through a transient dissolution event in the deep sea. The magnitude of change in preformed nutrients suggested by the North Pacific data would have accounted for a majority of the observed decrease in glacial atmospheric pCO2.

Carbonate minerals, uranium and thorium concentration and U-Th ages of sediments from ODP Leg 166 sites

We have performed U-Th isotope analyses on pure aragonite samples from the upper sections of Leg 166 cores to assign each aragonite-rich sediment package to the correct sea-level highstand. The uppermost sediment package from each of the four sites investigated (Sites 1003, 1005, 1006, and 1007) yielded a Holocene U-Th age. Sediment packages from deeper in the cores have suffered diagenesis. This diagenesis consists of significant U loss (up to 40%) in the site nearest the platform (Site 1005), slight U gain in sites further from the platform, and continuous loss of pure 234U caused by alpha recoil at all sites. The difference in diagenesis between the sites can be explained by the different fluid-flow histories they have experienced. Site 1005 is sufficiently close to the platform to have probably experienced a change in flow direction whenever the banks have flooded or become exposed. Other sites have probably experienced continuous flow into the sediment. Although diagenesis prevents assignment of accurate ages, it is sufficiently systematic that it can be corrected for and each aragonite-rich package assigned to a unique highstand interval. Site 1005 has sediment packages from highstands associated with marine isotope Stages 1, 5, 7, 9, and 11. Site 1006 is similar, except that the Stage 7 highstand is missing, at least in Hole 1006A. Site 1003 has sediment only from Stage 1 and 11 highstands within the U-Th age range. And Site 1007 has sediment only from the stage 1 highstand. This information will allow the construction of better age models for these sites. No high-aragonite sediments are seen for Stage 3 or Substages 5a and 5c. Unless rather unusual erosion has occurred, this indicates that the banks did not flood during these periods. If true, this would require the sea level for Substages 5a and 5c to have remained at least ~10 m lower than today.

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.

Ba distribution in surface sediments of the Southern Ocean

We present excess Ba (Baxs) data (i.e., total Ba corrected for lithogenic Ba) for surface sediments from a north-south transect between the Polar Front Zone and the northern Weddell Gyre in the Atlantic sector and between the Polar Front Zone and the Antarctic continent in the Indian sector. Focus is on two different processes that affect excess Ba accumulation in the sediments: sediment redistribution and excess Ba dissolution. The effect of these processes needs to be corrected for in order to convert accumulation rate into vertical rain rate, the flux component that can be linked to export production. In the Southern Ocean a major process affecting Ba accumulation rate is sediment focusing, which is corrected for using excess 230Th. This correction, however, may not always be straightforward because of boundary scavenging effects. A further major process affecting excess Ba accumulation is barite dissolution during exposure at the sediment-water column interface. Export production estimates derived from excess 230Th and barite dissolution corrected Baxs accumulation rates (i.e., excess Ba vertical rain rates) are of the same magnitude but generally larger than export production estimates based on water column proxies (234Th-deficit in the upper water column; particulate excess Ba enrichment in the mesopelagic water column). We believe export production values based on excess Ba vertical rain rate might be overestimated due to inaccurate assessment of the Baxs preservation rate. Barite dissolution has, in general, been taken into account by relating it to exposure time before burial depending on the rate of sediment accumulation. However, the observed decrease of excess Ba content with increasing water column depth (or increasing hydrostatic pressure) illustrates the dependence of barite preservation on degree of saturation in the deep water column in accordance with available thermodynamic data. Therefore correction for barite dissolution would not be appropriate by considering only exposure time of the barite to some uniformly undersaturated deep water but requires also that regional differences in degree of undersatuation be taken into account.