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.

Mg/Ca ratios in planktonic foraminifera

The primary Mg/Ca ratio of foraminiferal shells is a potentially valuable paleoproxy for sea surface temperature (SST) reconstructions. However, the reliable extraction of this ratio from sedimentary calcite assumes that we can overcome artifacts related to foraminiferal ecology and partial dissolution, as well as contamination by secondary calcite and clay. The standard batch method for Mg/Ca analysis involves cracking, sonicating, and rinsing the tests to remove clay, followed by chemical cleaning, and finally acid-digestion and single-point measurement. This laborious procedure often results in substantial loss of sample (typically 30-60%). We find that even the earliest steps of this procedure can fractionate Mg from Ca, thus biasing the result toward a more variable and often anomalously low Mg/Ca ratio. Moreover, the more rigorous the cleaning, the more calcite is lost, and the more likely it becomes that any residual clay that has not been removed by physical cleaning will increase the ratio. These potentially significant sources of error can be overcome with a flow-through (FT) sequential leaching method that makes time- and labor-intensive pretreatments unnecessary. When combined with time-resolved analysis (FT-TRA) flow-through, performed with a gradually increasing and highly regulated acid strength, produces continuous records of Mg, Sr, Al, and Ca concentrations in the leachate sorted by dissolution susceptibility of the reacting material. Flow-through separates secondary calcite from less susceptible biogenic calcite and clay, and further resolves the biogenic component into primary and more resistant fractions. FT-TRA reliably separates secondary calcite (which is not representative of original life habitats) from the more resistant biogenic calcite (the desired signal) and clay (a contaminant of high Mg/Ca, which also contains Al), and further resolves the biogenic component into primary and more resistant fractions that may reflect habitat or other changes during ontogeny. We find that the most susceptible fraction of biogenic calcite in surface dwelling foraminifera gives the most accurate value for SST and therefore best represents primary calcite. Sequential dissolution curves can be used to correct the primary Mg/Ca ratio for clay, if necessary. However, the temporal separation of calcite from clay in FT-TRA is so complete that this correction is typically <=2%, even in clay-rich sediments. Unlike hands-on batch methods, that are difficult to reproduce exactly, flow-through lends itself to automation, providing precise replication of treatment for every sample. Our automated flow-through system can process 22 samples, two system blanks, and 48 mixed standards in <12 hours of unattended operation. FT-TRA thus represents a faster, cheaper, and better way to determine Mg/Ca ratios in foraminiferal calcite.

Age model and elemental data of DSDP Holes 48-401 and 80-549

A growing body of geologic evidence suggests that emplacement of the North Atlantic Igneous Province (NAIP) played a major role in global warming during the early Paleogene as well as in the transient Paleocene-Eocene thermal maximum (PETM) event. A ~5 million year record of major and trace element abundances spanning 56 to 51 Ma at Deep Sea Drilling Project Sites 401 and 549 confirms that the majority of NAIP volcanism occurred as subaerial flows. Thus the trace element records provide constraints on the nature and scope of the environmental impact of the NAIP during the late Paleocene-early Eocene interval. Subaerial volcanism would have injected mantle CO2 directly into the atmosphere, resulting in a more immediate increase in atmospheric greenhouse gas abundances than CO2 input through submarine volcanism. The lack of significant hydrothermalism contradicts recently proposed mechanisms for thermally destabilizing methane hydrate reservoirs during the PETM. Any connection between NAIP volcanism and PETM warming had to occur through the atmosphere.

Epibenthic foraminifera stable isotope and planktic foraminifera Ba/Ca data of sediment core MD03-2664

Deep ocean circulation has been considered relatively stable during interglacial periods, yet little is known about its behavior on submillennial time scales. Using a subcentennially resolved epibenthic foraminiferal d13C record we show that North Atlantic Deep Water (NADW) influence was strong at the onset of the last interglacial period and then interrupted by several prominent, centennial-scale reductions. These NADW transients occurred during periods of increased ice rafting and southward expansions of polar water influence, suggesting that a buoyancy threshold for convective instability was triggered by freshwater and circum-Arctic cryosphere changes. The deep Atlantic chemical changes were similar in magnitude to those associated with glaciations, implying that the canonical view of a relatively stable interglacial circulation may not hold for conditions warmer/fresher than at present.

Mg/Ca ratios of Globigerinoides ruber of sediment core GeoB4905-4

Here we present evidence that the Holocene African monsoon system (AMS) varied in response to the eastern equatorial Atlantic sea-surface temperature (SST). Several short-term episodes of decreased moisture availability as a result of low eastern equatorial Atlantic SST are suggested by planktonic foraminiferal Mg/Ca ratios. These episodes promoted a weakening of the AMS and thus determined the timing and intensity of arid periods. Local sea-surface salinities also reveal regional patterns of precipitation in equatorial western Africa. The high eastern equatorial Atlantic SSTs occur in concert with seasonally increased insolation at low latitudes, suggesting a strong response of African monsoonal precipitation to oceanic conditions at low latitudes.

Mg/Ca values for planktonic foraminifera N. pachyderma and G. bulloides from ocean sediment core MD02-2496 on the Vancouver margin, Northeastern Pacific Ocean

A new, high-resolution planktonic foraminiferal Mg/Ca-based ocean temperature record has been generated for deep sea core MD02-2496, sited offshore of Vancouver Island, Western Canada during the last deglaciation (21-12 ka). The relationship between Cordilleran Ice Sheet (CIS) retreat and changing regional ocean temperatures has been reconstructed through glaciomarine sediments in MD02-2496 that capture tidewater glacier response to surface ocean thermal forcing. At CIS maximum extent, the marine margin of the ice sheet advanced onto the continental shelf. During this interval, ocean temperatures recorded by surface ocean dwelling Globigerina bulloides remained a relatively constant ~7.5°C while subsurface dwelling Neogloboquadrina pachyderma (s.) recorded temperatures of ~5°C. These ocean temperatures were sufficiently warm to induce significant melt along the tidewater ice terminus similar to modern Alaskan tidewater glacial systems. During the deglacial retreat of the CIS, the N. pachyderma temperature record shows two distinct warming steps of ~2 and 2.5°C between 17.2-16 and 15.5-14 ka respectively, coincident with ice rafting events from the CIS, while G. bulloides records an ~3°C warming from 15 to14 ka. We hypothesize that submarine melting resulting from relatively warm ocean temperatures was an important process driving ice removal from CIS tidewater glaciers during the initial stages of deglaciation.