Age and oxygen isotope data for bulk carbonate from DSDP Sites 41-366 and 72-516 and ODP Sites 111-677A and 130-807

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.

Magnesium isotope ratios of pore-fluids and dolomites

Magnesium concentrations in deep-sea sediment pore-fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust. To better characterize and differentiate these processes, we have measured magnesium isotopes in pore-fluids and sediment samples from Ocean Drilling Program sites (1082, 1086, 1012, 984, 1219, and 925) that span a range of oceanographic settings. At all sites, magnesium concentrations decrease with depth. At sites where diagenetic reactions are dominated by the respiration of organic carbon, pore-fluid d26Mg values increase with depth by as much as 2 per mil. Because carbonates preferentially incorporate 24Mg (low d26Mg), the increase in pore-fluid d26Mg values at these sites is consistent with the removal of magnesium in Mg-carbonate (dolomite). In contrast, at sites where the respiration of organic carbon is not important and/or weatherable minerals are abundant, pore-fluid d26Mg values decrease with depth by up to 2 per mil. The decline in pore-fluid d26Mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore-fluid. The identity of this enriched magnesium sink is likely clay minerals. Using a simple 1D diffusion-advection-reaction model of pore-fluid magnesium, we estimate rates of net magnesium uptake/removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites. Independent estimates of magnesium isotope fractionation during dolomite precipitation from measured d26Mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites, suggesting that local exchange of magnesium between sediment and pore-fluid at these sites can be neglected. Our results indicate that the magnesium incorporated in dolomite is 2.0-2.7 per mil depleted in d26Mg relative to the precipitating fluid. Assuming local exchange of magnesium is minor at the rest of the studied sites, our results suggest that magnesium incorporated into clay minerals is enriched in d26Mg by 0 per mil to +1.25 per mil relative to the precipitating fluid. This work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources/sinks in low-temperature aqueous systems.