(Table 1) Comparison between bulk ICP-OES measurements and LA-ICP-MS analyses for Mg/Ca and Sr/Ca ratios of Globigerinoides sacculifer from ODP Hole 165-1000A

We constructed a high-resolution Mg/Ca record on the planktonic foraminifer Globigerinoides sacculifer in order to explore the change in sea surface temperature (SST) due to the shoaling of the Isthmus of Panama as well as the impact of secondary factors like diagenesis and large salinity fluctuations. The study covers the latest Miocene and the early Pliocene (5.6-3.9 Ma) and was combined with d18O to isolate changes in sea surface salinity (SSS). Before 4.5 Ma, SSTMg/Ca and SSS show moderate fluctuations, indicating a free exchange of surface ocean water masses between the Pacific and the Atlantic. The increase in d18O after 4.5 Ma represents increasing salinities in the Caribbean due to the progressive closure of the Panamanian Gateway. The increase in Mg/Ca toward values of maximum 7 mmol/mol suggests that secondary influences have played a significant role. Evidence of crystalline overgrowths on the foraminiferal tests in correlation with aragonite, Sr/Ca, and productivity cyclicities indicates a diagenetic overprint on the foraminiferal tests. Laser ablation inductively coupled plasma-mass spectrometry analyses, however, do not show significantly increased Mg/Ca ratios in the crystalline overgrowths, and neither do calculations based on pore water data conclusively result in significantly elevated Mg/Ca ratios in the crystalline overgrowths. Alternatively, the elevated Mg/Ca ratios might have been caused by salinity as the d18O record of Site 1000 has been interpreted to represent large fluctuations in SSS, and cultivating experiments have shown an increase in Mg/Ca with increasing salinity. We conclude that the Mg/Ca record <4.5 Ma can only reliably be considered for paleoceanographical purposes when the minimum values, not showing any evidence of secondary influences, are used, resulting in a warming of central Caribbean surface water masses after 4.5 Ma of ~2°C.

Thallium isotope composition in pyrites

This paper presents the first study of Tl isotopes in early diagenetic pyrite. Measurements from two sections deposited during the Toarcian Ocean Anoxic Event (T-OAE, ~183 Ma) are compared with data from Late Neogene (<10 Ma) pyrite samples from ODP legs 165 and 167 that were deposited in relatively oxic marine environments. The Tl isotope compositions of Late Neogene pyrites are all significantly heavier than seawater, which most likely indicates that Tl in diagenetic pyrite is partially sourced from ferromanganese oxy-hydroxides that are known to display relatively heavy Tl isotope signatures. One of the T-OAE sections from Peniche in Portugal displays pyrite thallium isotope compositions indistinguishable from Late Neogene samples, whereas samples from Yorkshire in the UK are depleted in the heavy isotope of Tl. These lighter compositions are best explained by the lack of ferromanganese precipitation at the sediment-water interface due to the sulfidic (euxinic) conditions thought to be prevalent in the Cleveland Basin where the Yorkshire section was deposited. The heavier signatures in the Peniche samples appear to result from an oxic water column that enabled precipitation of ferromanganese oxy-hydroxides at the sediment-water interface. The Tl isotope profile from Yorkshire is also compared with previously published molybdenum isotope ratios determined on the same sedimentary succession. There is a suggestion of an anti-correlation between these two isotope systems, which is consistent with the expected isotope shifts that occur in seawater when marine oxic (ferromanganese minerals) fluxes fluctuate. The results outlined here represent the first evidence that Tl isotopes in early diagenetic pyrite have potential to reveal variations in past ocean oxygenation on a local scale and potentially also for global oceans. However, much more information about Tl isotopes in different marine environments, especially in anoxic/euxinic basins, is needed before Tl isotopes can be confidently utilized as a paleo-redox tracer.