Expanded GHOST database

In this study we review a global set of alkenone- and foraminiferal Mg/Ca-derived sea surface temperatures (SST) records from the Holocene and compare them with a suite of published Eemian SST records based on the same approach. For the Holocene, the alkenone SST records belong to the actualized GHOST database (Kim, J.-H., Schneider R.R., 2004). The actualized GHOST database not only confirms the SST changes previously described but also documents the Holocene temperature evolution in new oceanic regions such as the Northwestern Atlantic, the eastern equatorial Pacific, and the Southern Ocean. A comparison of Holocene SST records stemming from the two commonly applied paleothermometry methods reveals contrasting - sometimes divergent - SST evolution, particularly at low latitudes where SST records are abundant enough to infer systematic discrepancies at a regional scale. Opposite SST trends at particular locations could be explained by out-of-phase trends in seasonal insolation during the Holocene. This hypothesis assumes that a strong contrast in the ecological responses of coccolithophores and planktonic foraminifera to winter and summer oceanographic conditions is the ultimate reason for seasonal differences in the origin of the temperature signal provided by these organisms. As a simple test for this hypothesis, Eemian SST records are considered because the Holocene and Eemian time periods experienced comparable changes in orbital configurations, but had a higher magnitude in insolation variance during the Eemian. For several regions, SST changes during both interglacials were of a similar sign, but with higher magnitudes during the Eemian as compared to the Holocene. This observation suggests that the ecological mechanism shaping SST trends during the Holocene was comparable during the penultimate interglacial period. Although this "ecology hypothesis" fails to explain all of the available results, we argue that any other mechanism would fail to satisfactorily explain the observed SST discrepancies among proxies.

Geochemistry and P and Fe fractionation in anoxic sediments

We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (~94 Ma) and the Paleocene-Eocene thermal maximum (?55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO3 contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO3 can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.

Sediment geochemistry PASOM research cruise (2009) - Murray Ridge region, northern Arabian Sea

In this study, we investigate phosphorus (P) and iron (Fe) cycling in sediments along a depth transect from within to well below the oxygen minimum zone (OMZ) in the northern Arabian Sea (Murray Ridge). Pore-water and solid-phase analyses show that authigenic formation of calcium phosphate minerals (Ca-P) is largely restricted to where the OMZ intersects the seafloor topography, likely due to higher depositional fluxes of reactive P. Nonetheless, increased ratios of organic carbon to organic P (Corg/Porg) and to total reactive P (Corg/Preactive) in surface sediments indicate that the overall burial efficiency of P relative to Corg decreases under the low bottom water oxygen concentrations (BWO) in the OMZ. The relatively constant Fe/Al ratio in surface sediments along the depth transect suggest that corresponding changes in Fe burial are limited. Sedimentary pyrite contents are low throughout the ~25 cm sediment cores at most stations, as commonly observed in the Arabian Sea OMZ. However, pyrite is an important sink for reactive Fe at one station in the OMZ. A reactive transport model (RTM) was applied to quantitatively investigate P and Fe diagenesis at an intermediate station at the lower boundary of the OMZ (bottom water O2: ~14 µmol/L). The RTM results contrast with earlier findings in showing that Fe redox cycling can control authigenic apatite formation and P burial in Arabian Sea sediment. In addition, results suggest that a large fraction of the sedimentary Ca-P is not authigenic, but is instead deposited from the water column and buried. Dust is likely a major source of this Ca-P. Inclusion of the unreactive Ca-P pool in the Corg/P ratio leads to an overestimation of the burial efficiency of reactive P relative to Corg along the depth transect. Moreover, the unreactive Ca-P accounts for ~85% of total Ca-P burial. In general, our results reveal large differences in P and Fe chemistry between stations in the OMZ, indicating dynamic sedimentary conditions under these oxygen-depleted waters.

Stable isotope data and calcification temperature from planktic foraminifera in sediment core BOFS31/1K

Determining the past record of temperature and salinity of ocean surface waters is essential for understanding past changes in climate, such as those which occur across glacial-interglacial transitions. As a useful proxy, the oxygen isotope composition (delta18O) of calcite from planktonic foraminifera has been shown to reflect both surface temperature and seawater delta18O, itself an indicator of global ice volume and salinity (Shackleton, 1974; Rostek et al., 1993, doi:10.1038/364319a0). In addition, magnesium/calcium (Mg/Ca) ratios in foraminiferal calcite show a temperature dependence (Nürnberg, 1995, doi:10.2113/gsjfr.25.4.350; Nürnberg et al., 1996, doi:10.1016/0016-7037(95)00446-7; Lea et al., 1999, doi:10.1016/S0016-7037(99)00197-0) due to the partitioning of Mg during calcification. Here we demonstrate, in a field-based calibration experiment, that the variation of Mg/Ca ratios with temperature is similar for eight species of planktonic foraminifera (when accounting for Mg dissolution effects). Using a multi-species record from the Last Glacial Maximum in the North Atlantic Ocean we found that past temperatures reconstructed from Mg/Ca ratios followed the two other palaeotemperature proxies: faunal abundance (CLIMAP, 1981; Mix et al., 1999, doi:10.1029/1999PA900012) and alkenone saturation (Müller et al., 1998, doi:10.1016/S0016-7037(98)00097-0 ). Moreover, combining Mg/Ca and delta18O data from the same faunal assemblage, we show that reconstructed surface water delta18O from all foraminiferal species record the same glacial-interglacial change-representing changing hydrography and global ice volume. This reinforces the potential of this combined technique in probing past ocean-climate interactions.

Sable oxygen isotope and Mg/Ca ratios of planktonic foraminifera from DSDP Hole 31-292

This study presents new evidence of when and how the Western Pacific Warm Pool (WPWP) was established in its present form. We analyzed planktic foraminifera, oxygen isotopes, and Mg/Ca ratios in upper Miocene through Pleistocene sediments collected at Deep Sea Drilling Program (DSDP) Site 292. These data were then compared with those reported from Ocean Drilling Program (ODP) Site 806. Both drilling sites are located in the western Pacific Ocean. DSDP Site 292 is located in the northern margin of the modern WPWP and ODP Site 806 near the center of the WPWP. Three stages of development in surface-water conditions are identified in the region using planktic foraminferal data. During the initial stage, from 8.5 to 4.4 Ma, Site 806 was overlain by warm surface water but Site 292 was not, as indicated by the differences in faunal compositions and sea-surface temperature (SST) between the two sites. In addition, the vertical thermal gradient at Site 292 was weak during this period, as indicated by the small differences in the delta18O values between Globigerinoides sacculifer and Pulleniatina spp. During stage two, from 4.4 to 3.6 Ma, the SST at Site 292 rapidly increased to 27 °C, but the vertical thermal gradient had not yet be strengthened, as shown by Mg/Ca ratios and the presence of both mixed-layer dwellers and thermocline dwellers. Finally, a warm mixed layer with a high SST ca. 28 °C and a strong vertical thermal gradient were established at Site 292 by 3.6 Ma. This event is marked by the dominance of mixed-layer dwellers, a high and stable SST, and a larger differences in the delta18O values between G. sacculifer and Pulleniatina spp. Thus, evidence of surface-water evolution in the western Pacific suggests that Site 292 came under the influence of the WPWP at 3.6 Ma. The northward expansion of the WPWP from 4.4 to 3.6 Ma and the establishment of the modern WPWP by 3.6 Ma appear to be closely related to the closure of the Indonesian and Central American seaways.