Calcium isotope ratios from marine barite and carbonate over Paleocene-Eocene Boundary (ODP Sites 1212 and 1221)

Carbonates are invaluable archives of the past, and have been used extensively to reconstruct paleoclimate and paleoceanographic conditions over geologic time scales. Such archives are susceptible to diagenetic alteration via dissolution, recrystallization and secondary precipitation, particularly during ocean acidification events when intense dissolution can occur. Despite the importance of diagenesis on proxy fidelity, the effects of diagenesis on the calcium isotopic composition (d44Ca) of carbonates are unclear. Accordingly, bulk carbonate d44Ca was measured at high resolution in two Pacific deep sea sediment cores (ODP Sites 1212 and 1221) with considerably different dissolution histories over the Paleocene-Eocene Thermal Maximum (PETM, ~55 Ma). The d44Ca of marine barite was also measured at the deeper Site 1221, which experienced severe carbonate dissolution during the PETM. Large (~0.8 per mil) variations in bulk carbonate d44Ca occur in the deeper site near the peak carbon isotope excursion, and are correlated with a large drop in carbonate weight percent. Such an effect is seen in neither the 1221 barite record nor the bulk carbonate record at the shallower, less dissolved Site 1212. We contend that ocean chemical changes associated with the abrupt and massive carbon release into the ocean-atmosphere system and subsequent ocean acidification at the PETM affected the bulk carbonate d44Ca record via diagenesis in the sedimentary column. Such changes are considerable, and need to be taken into account when interpreting and modeling Ca isotope data over extreme climatic events associated with ocean chemical evolution.

(Table 1) Oxygen and carbon isotope data of bulk carbonate and foraminiferal species across the Cretaceous/Tertiary boundary at ODP Site 119-738

In low and middle latitudes, the Cretaceous/Tertiary boundary is marked by a sudden and pronounced decrease in d13C values of near-surface-water carbonates and a reduction in the surface-to-bottom d13C gradient. These isotopic data have been interpreted as evidence of a decline in surface-water productivity that was responsible for the extinction of many planktic foraminiferal species and other marine organisms at or near the K/T boundary. We present planktic and benthic foraminiferal isotopic data from two almost biostratigraphically complete sections at Ocean Drilling Program Site 738 in the antarctic Indian Ocean and at Nye Kløv in Denmark. These data suggest that planktic carbonate d13C values in high latitudes may not have decreased dramatically at the K/T boundary; thus, surface-water productivity may not have been reduced as much as in low and middle latitudes. Comparison of the records of Site 738 with those of ODP Sites 690 and 750 indicates a pronounced decline in d13C values of planktic and benthic foraminifera and fine-fraction/bulk carbonate ~200 000 yr after the K/T boundary. This reflects a regional shift in the carbon isotopic composition of oceanic total dissolved carbon (TDC) and correlates with a similar change in benthic foraminiferal d13C values at mid- and low-latitude Deep Sea Drilling Project Sites 527 and 577. This oceanographic event was followed by the ecosystem's global recovery ~500 000 yr after the K/T boundary. These data suggest that the environmental effects of the K/T boundary may have been less severe in the high-latitude oceans than in tropical and subtropical regions.