ALBERT

Description: New Sr isotopic and concentration analyses of bulk carbonate and porewaters from a carbonate-rich Miocene section sampled at DSDP Site 575 are reported and used, along with our earlier data from a section of similar age at DSDP Site 590B, in a numerical model to determine for each site the rate of Sr exchange during diagenesis and the degree to which this amount of exchange has shifted the 87Sr/86Sr of the bulk carbonate from the ratio each increment of sediment had when first deposited. Despite the fact that the two sites have very different water depth (4536 m at 575 vs. 1299 m at 590B), different sedimentation rate (~10 m/My at 575 vs. ~40 m/My at 590B), and significantly different porewater Sr(2+) gradients, we find that the rate of Sr exchange as a function of sediment age is almost indistinguishable between the two sites. The rate of Sr exchange determined at the two sites is such that the resulting shift in bulk carbonate 87Sr/86Sr due to diagenesis is small compared to the total range of 87Sr/86Sr values measured, but large compared to the analytical uncertainty of the individual isotopic ratio measurements. By taking this shift into account we reconstruct the original 87Sr/86Sr of each increment of carbonate sampled, which when plotted as a function of age becomes our best estimate of the Sr isotopic evolution of seawater. Because Sr is very well mixed in the ocean, at any given time there is a single worldwide value of seawater 87Sr/86Sr. Therefore, if we are quantitatively accounting for the effect Sr exchange, we should find the same seawater evolution curve regardless of what DSDP Site is used. When we compare the observed bulk carbonate 87Sr/86Sr vs. age at the two sites they are seen to differ by amounts that are sometimes large compared to the analytical uncertainties of the measurements. However, when these data are corrected for the post-depositional Sr isotopic shifts predicted by our diagenetic model, we find almost perfect agreement. This agreement suggests that we have made a realistic determination of the rate of Sr exchange and its consequences in terms of shifting the 87Sr/86Sr of the bulk carbonate, and more importantly, that Sr isotopes can be used to correlate marine sediments with an accuracy comparable to the very small analytical uncertainties of modern isotopic measurements.

Description: A numerical model which describes oxygen isotope exchange during burial and recrystallization of deep-sea carbonate is used to obtain information on how sea surface temperatures have varied in the past by correcting measured d18O values of bulk carbonate for diagenetic overprinting. Comparison of bulk carbonate and planktonic foraminiferal d18O records from ODP site 677A indicates that the oxygen isotopic composition of bulk carbonate does reflect changes in sea surface temperature and d18O. At ODP Site 690, we calculate that diagenetic effects are small, and that both bulk carbonate and planktonic foraminiferal d18O records accurately reflect Paleogene warming of high latitude surface oceans, biased from diagenesis by no more than 1°C. The same is likely to be true for other high latitude sites where sedimentation rates are low. At DSDP sites 516 and 525, the effects of diagenesis are more significant. Measured d18O values of Eocene bulk carbonates are more than 2‰ lower at deeply buried site 516 than at site 525, consistent with the model prediction that the effects of diagenesis should be proportional to sedimentation rate. Model-corrections reconcile the differences in the data between the two sites; the resulting paleotemperature reconstruction indicates a 4°C cooling of mid-latitude surface oceans since the Eocene. At low latitudes, the contrast in temperature between the ocean surface and bottom makes the carbonate d180 values particularly sensitive to diagenetic effects; most of the observed variations in measured d18O values are accounted for by diagenetic effects rather than by sea surface temperature variations. We show that the data are consistent with constant equatorial sea surface temperatures through most of the Cenozoic, with the possible exception of the early Eocene, when slightly higher temperatures are indicated. We suggest that the lower equatorial sea surface temperatures for the Eocene and Oligocene reported in other oxygen isotope studies are artifacts of diagenetic recrystallization, and that it is impossible to reconstruct accurately equatorial sea surface temperatures without explicitly accounting for diagenetic overprinting.