Calibration and application of B/Ca, Cd/Ca, and d11B in Neogloboquadrina pachyderma (sinistral)

The North Atlantic and Norwegian Sea are prominent sinks of atmospheric CO2 today, but their roles in the past remain poorly constrained. In this study, we attempt to use B/Ca and d11B ratios in the planktonic foraminifera Neogloboquadrina pachyderma (sinistral variety) to reconstruct subsurface water pH and pCO2 changes in the polar North Atlantic during the last deglaciation. Comparison of core-top results with nearby hydrographic data shows that B/Ca in N. pachyderma (s) is mainly controlled by seawater [B(OH)4]?/[HCO3]? with a roughly constant partition coefficient (KD =([B/Ca]of CaCO3)/([B(OH)4]-/[HCO3]-)of seawater) of 1.48 ± 0.15 * 10**-3 (2sigma), and d11B in this species is offset below d11B of the borate in seawater by 3.38 ± 0.71 per mil (2sigma). These values represent our best estimates with the sparse available hydrographic data close to our core-tops. More culturing and sediment trap work is needed to improve our understanding of boron incorporation into N. pachyderma (s). Application of a constant KD of 1.48 * 10**-3 to high resolution N. pachyderma (s) B/Ca records from two adjacent cores off Iceland shows that subsurface pCO2 at the habitat depth of N. pachyderma (s) (~50 m) generally followed the atmospheric CO2 trend but with negative offsets of ~10-50 ppmv during 19-10 ka. These B/Ca-based reconstructions are supported by independent estimates from low-resolution d11B measurements in the same cores. We also calibrate and apply Cd/Ca in N. pachyderma (s) to reconstruct nutrient levels for the same down cores. Like today's North Atlantic, past subsurface pCO2 variability off Iceland was significantly correlated with nutrient changes that might be linked to surface nutrient utilization and mixing within the upper water column. Because surface pCO2 (at 0 m water depth) is always lower than at deeper depths and if the application of a constant KD is valid, our results suggest that the polar North Atlantic has remained a CO2 sink during the calcification seasons of N. pachyderma (s) over the last deglaciation.

Cd and d13C reconstruction for the LGM and Holocene in Brazil Margin sediment cores

Paleoceanographic studies using benthic foraminiferal Cd as a nutrient tracer have provided a robust means of reconstructing glacial Atlantic Ocean water mass geometry, but a paucity of data from the South Atlantic above 1200 m has limited investigation of Antarctic Intermediate Water (AAIW) configuration and formation. A new Cd depth profile from Brazil margin sediments suggests that AAIW penetrated northward at 1100 m to at least 27°S in the glacial Atlantic. It exhibited substantially reduced d13Cas values, confirming preliminary evidence that this AAIW was unique to the glacial Atlantic and that it formed differently than today, with less atmospheric contact.

Seawater Cd reconstruction for the western subtropical South Atlantic

Benthic foraminiferal Cd/Ca from an intermediate depth, western South Atlantic core documents the history of southward penetration of North Atlantic Intermediate Water (NAIW). Cd seawater estimates (CdW) for the last glacial are consistent with the production of NAIW and its export into the South Atlantic. At ~14.5 ka concurrently with the onset of the Bølling-Allerød to Younger Dryas cooling, the NAIW contribution to the South Atlantic began to decrease, marking the transition from a glacial circulation pattern to a Younger Dryas circulation. High CdW in both the deep North Atlantic and the intermediate South Atlantic imply reduced export of deep and intermediate water during the Younger Dryas and a significant decrease in northward oceanic heat transport. A modern circulation was achieved at ~9 ka, concurrently with the establishment of Holocene warmth in the North Atlantic region, further supporting a close linkage between deepwater variability and North Atlantic climate.

Benthic foraminiferal Cd/Ca and isotope record from the South Atlantic

A depth transect of cores from 1268 to 3909 m water depth in the western South Atlantic are ideally situated to monitor the interocean exchange of deep water and variations in the relative strength of northern and southern sources of deep water production. Benthic foraminiferal Cd/Ca and d13C data suggest that Glacial North Atlantic Intermediate Water (GNAIW) extended at least as far south as 28°S in the western South Atlantic. The core of nutrient-depleted water was situated at ~1500 m, above and below water masses with higher nutrient concentrations. When examined in conjunction with published paired Cd/Ca and d13C from intermediate depth cores from other basins, it appears that the extent of GNAIW influence on the intermediate waters of the world's oceans was less than suggested previously. Differentiating among possible pathways for the glacial deep ocean (>3 km) requires a better understanding of the controls on Cd/Ca and d13C values of benthic foraminifera.

Calcite saturation and yield and Mg/Ca, Mn/Ca, Al/Ca, Fe/Ca for four species of planktic foraminifera cleaned using Mg-cleaning and Cd-cleaning methods

Four species of planktic foraminifera from core-tops spanning a depth transect on the Ontong Java Plateau were prepared for Mg/Ca analysis both with (Cd-cleaning) and without (Mg-cleaning) a reductive cleaning step. Reductive cleaning caused etching of foraminiferal calcite, focused on Mg-rich inner calcite, even on tests which had already been partially dissolved at the seafloor. Despite corrosion, there was no difference in Mg/Ca of Pulleniatina obliquiloculata between cleaning methods. Reductive cleaning decreased Mg/Ca by an average (all depths) of ~ 4% for Globigerinoides ruber white and ~ 10% for Neogloboquadrina dutertrei. Mg/Ca of Globigerinoides sacculifer (above the calcite saturation horizon only) was 5% lower after reductive cleaning. The decrease in Mg/Ca due to reductive cleaning appeared insensitive to preservation state for G. ruber, N. dutertrei and P. obliquiloculata. Mg/Ca of Cd-cleaned G. sacculifer appeared less sensitive to dissolution than that of Mg-cleaned. Mg-cleaning is adequate, but SEM and contaminants (Al/Ca, Fe/Ca and Mn/Ca) show that Cd-cleaning is more effective for porous species. A second aspect of the study addressed sample loss during cleaning. Lower yield after Cd-cleaning for G. ruber, G. sacculifer and N. dutertrei confirmed this to be the more aggressive method. Strongest correlations between yield and Delta[CO3^2-] in core-top samples were for Cd-cleaned G. ruber (r = 0.88, p = 0.020) and Cd-cleaned P. obliquiloculata (r = 0.68, p = 0.030). In a down-core record (WIND28K) correlation, r, between yield values > 30% and dissolution index, XDX, was -0.61 (p = 0.002). Where cleaning yield < 30% most Mg-cleaned Mg/Ca values were biased by dissolution.

Sedimentology and Cd/Ca ratios of benthic foraminifera from ODP Site 172-1060 in the western Nort Atlantic

The Western Boundary Undercurrent (WBUC), off eastern America, is an important component of the Atlantic Meridional Overturning circulation and is the principal route for southward transport of North Atlantic waters and southward return of Southern Source Water (SSW). Here a direct flow speed proxy (mean grain size of the sortable silt) is used to infer the vigour of flow of the palaeo-WBUC at Blake Outer Ridge, (ODP Site 1060, depth 3481 m) during Marine Isotope Stage (MIS) 3. The overall shape of the flow speed proxy record shows a complex pattern of variability, with generally more vigorous flow and larger-scale flow variations between 35 and 60 ka than in the younger part of MIS 3 and MIS 2 (b35 ka). Six events of reduced bottom flow vigour (Slow Events, SEs) occur. These appear uncorrelated with Heinrich events, but are instead synchronous with the warming phases of Antarctic Warm Events A-1 to A-4 (with one new one, A-1a and one poorly defined, 'A-0'). This indicates that Antarctic climate exerts a stronger control on deep flow vigour in the North Atlantic during MIS 3 than Northern Hemisphere climate. The correspondence of SEs with Antarctic warming suggests a weaker WBUC flow due to reduced volume flux at SSW source or reduced SSW density. Because the variability of the lower limb of the WBUC was not connected to sharp North Atlantic changes in temperature, it is unlikely that the Dansgaard/Oeschger cycles were associated with a mode of MOC variation involving wholeocean overturn, but more likely with perturbations of only the shallow Glacial Gulf Stream-Glacial Northern Source Intermediate Water cell. Nutrient proxies (benthic carbon isotopes and Cd/Ca of Uvigerina peregrina) at this site show similar trends to the GRIP delta18O record. This correlation has previously been attributed mainly to hydrographic and flow changes but is here shown to be better explained by variations in surface ocean productivity and subsequent decomposition of 12C rich organic material on the sea floor.