Ba/Ca ratios in benthic foraminifera from recent core tops

The carbon isotope ratio (delta13C) and cadmium content (Cd/Ca) of benthic foraminifera shells have been used to reconstruct deep-water circulation patterns of the glacial oceans. These tracers co-vary with phosphorus in the modern ocean because they are nearly quantitatively regenerated from sinking biological debris in the upper water column. Hence they can be used to reconstruct the distribution of labile nutrients in glacial water masses. Independent constraints on glacial deep-ocean circulation patterns could be provided by a tracer of the distribution of silica and alkalinity, the deeply regenerated constituents of planktonic hard parts. Barium shares key aspects of its behaviour with these refractory nutrients because it is removed from solution in surface waters and incorporated into sinking particles which slowly dissolve deep in the water column and in the sediments. The fractionation of Ba between deep-water masses of the major ocean basins is largely controlled by thermohaline circulation patterns, so Ba conforms to different boundary conditions from Cd and 13C. As Ba substitutes into trigonal carbonates, it is a potential palaeoceano-graphic tracer if the Ba content of foraminifera shells reflects ambient dissolved Ba concentrations. Here we present data from Recent core-top benthic foraminifera which indicate that the Ba content of some recent calcitic benthic foraminifera does co-vary with bottom-water Ba.

(Table 1) Cd/Ca and Mn/Ca ratios of benthic foraminifera from DSDP Hole 30-289

The late Miocene carbon shift (~6.2 Myr) -a 0.5-1.0 per mil, d13C decrease in benthic and planktonic foraminifera- has been ascribed to changes in global inventory, deep-ocean circulation, and/or productivity. Cadmium, d13C, and nutrients in the ocean are linked; comparison of d13C and Cd/Ca yields circulation and chemical inventory information not available from either alone. We determined Cd/Ca ratios in late Miocene benthic foraminifera from DSDP Site 289. Results include: (1) late Miocene Pacific Cd/Ca values fall between those of late Quaternary Atlantic and Pacific benthic foraminifera; (2) there are no systematic Cd/Ca offsets between Cibicidoides kullenbergi, Cibicidoides wuellerstorfi and Uvigerina spp.; and (3) there is a very slight Cd/Ca change coincident with d13C. Cd/Ca, slightly higher in younger, isotopically lighter samples, exhibits a smaller increase than predicted if circulation were the primary cause of the carbon shift. The carbon shift may have been due to a long-term shift in the steady-state carbon isotope input or to a change in the sedimentation of organic carbon relative to calcium carbonate.

Summary of boron isotope and Mg/Ca data

Biological productivity and carbon export in the equatorial Atlantic are thought to have been dramatically higher during the last glacial period than during the Holocene. Here we reconstruct the pH and CO2 content of surface waters from the eastern equatorial Atlantic Ocean over the past ~30 k.y. using the boron isotope composition of Globigerinoides ruber (a mixed-layer-dwelling planktic foraminifera). Our new record, combined with previously published data, indicates that during the last glacial, in contrast to today, a strong west to east gradient existed in the extent of air:sea equilibrium with respect to pCO2 (DeltapCO2), with the eastern equatorial Atlantic acting as a significant source of CO2 (+100 µatm) while the western Atlantic remained close to equilibrium (+25 µatm). This pattern suggests that a fivefold increase in the upwelling rate of deeper waters drove increased Atlantic productivity and large-scale regional cooling during the last glacial, but the higher than modern DeltapCO2 in the east indicates that export production did not keep up with enhanced upwelling of nutrients. However, the downstream decline of DeltapCO2 provides evidence that the unused nutrients from the east were eventually used for biologic carbon export, thereby effectively negating the impact of changes in upwelling on atmospheric CO2 levels. Our findings indicate that the equatorial Atlantic exerted a minimal role in contributing to lower glacial-age atmospheric CO2.

(Table A1) CaCO3 contents and Sr/Ca ratios in ODP Leg 130, 138 and 154

Strontium/calcium (Sr/Ca) ratios in bulk and foraminiferal calcite have been used to constrain the history of Sr/Ca in the oceans and to evaluate calcite diagenetic alteration. However bulk Sr/Ca records also may be influenced by differences in Sr uptake and/or in the diagenetic susceptibility of different calcium carbonate sedimentary components. We present data on the sediment size fraction and calcium carbonate distribution in bulk samples, Sr/Ca in a range of sedimentary size components, and Sr/Ca in bulk sediments. Ocean Drilling Program samples from sites on Ontong Java Plateau and Ceara Rise (in the western equatorial Pacific and Atlantic, respectively) and from sites in the eastern equatorial Pacific were selected to represent progressive stages in the diagenetic pathway from the sea floor through a range of burial depths equivalent to sediment ages of ~5.6, ~9.4, and ~37.1 Ma. Samples were subdivided by size to produce a unique data set of size-specific Sr/Ca ratios. Fine fraction (<45 ?m) Sr/Ca ratios are higher than those of all corresponding coarse fractions, indicating that fine nannofossil-dominated calcite has a Sr partition coefficient 1.3-1.5 times greater than that of coarse foraminifera-dominated calcite. Thus, absolute values of bulk Sr/Ca in contemporaneous samples reflect, in part, the ratio of fine to coarse calcite sedimentary components. Sr/Ca values in fine and coarse components also behave differently in their response to pre-burial dissolution and to recrystallization at depth. Coarse size components are sensitive to bottom water carbonate ion undersaturation, and they lose original Sr/Ca differences among contemporary samples over not, vert, similar10 my. In contrast, fine components recrystallize faster in more deeply buried samples. Interpretation of the historical Sr/Ca record is complicated by post-depositional diagenetic artifacts, and thus our data do not provide clear evidence of specific temporal changes in oceanic Sr/Ca ratios over the past 10 million years. This paper represents the first systematic attempt to examine trends in calcite Sr/Ca as a function of sediment size fraction and age.

Compilation of Mg/Ca ratios of Neogloboquadrina pachyderma (sinistral) and SST estimates from the northern North Atlantic

A map of estimated calcification temperatures of the planktic foraminifer Neogloboquadrina pachyderma sinistral (TNps) for the Nordic Seas and the northern North Atlantic for the Last Glacial Maximum was produced from oxygen isotopes with support of Mg/Ca ratios. To arrive at the reconstruction, several constraints concerning the plausible salinity and ?18O-fields were employed. The reconstruction indicates inflow of temperate waters in a wedge along the eastern border of the Nordic Seas and at least seasonally ice-free waters. The reconstruction from oxygen isotopes shows similarities with Mg/Ca based paleotemperatures in the southern and southeastern sector, while unrealistically high Mg/Ca values in the central Nordic Seas prevent the application of the method in this area. The oxygen isotope based reconstruction shows some agreement with temperature reconstructions based on the modern analogue technique, but with somewhat lower temperatures and a stronger internal gradient inside the Nordic Seas. All told, our results suggest a much more ice-free and dynamic high latitude ocean than the CLIMAP reconstruction.

Stable isotope and Mg/Ca ratio of sediment core GeoB12610-2

To reconstruct the still poorly understood thermocline fluctuations in the western tropical Indian Ocean, a sediment core located off Tanzania (GeoB12610-2; 04°49.00'S, 39°25.42'E, 399?m water depth) covering the last 35 ka was analysed. Mg/Ca-derived temperatures from the planktonic foraminifera Globigerinoides ruber (white) and Neogloboquadrina dutertrei indicate that the last glacial was ~2.5 °C colder in the surface waters and ~3.5 °C colder in the thermocline compared with the present day. The depth of the thermocline and thus the stratification of the water column were shallower during glacial periods and deepened during the deglaciation and Holocene. The increased inflow of Southern Ocean Intermediate Waters via 'ocean tunnels' appears to cool the thermocline from below, leading to a similarity between the thermocline record of GeoB12610-2 with the Antarctic EDML temperature curve during the glacial. With rising sea level and the corresponding greater inflow of Red Sea Waters and Indonesian Intermediate Waters, the proportion of Southern Ocean Intermediate Water within the South Equatorial Current is reduced and, by Holocene time, the correlation to Antarctica is barely traceable. Comparison with the eastern Indian Ocean reveals that the thermocline depth reverses from the last glacial to present.

(Table 3) Relative depth and age, CaCO3, d18O, d13C and Sr/Ca analysis from ODP Leg 130, 154 and 138

Interpretations of calcite strontium/calcium records in terms of ocean history and calcite diagenesis require distinguishing the effects on deep-sea calcite sediments of changes in ocean chemistry, of different mixes of calcite-depositing organisms as sediment contributors through time and space, and of the loss of Sr during diagenetic calcite recrystallization. In this paper Sr/Ca and d18O values of bulk calcium carbonate sediments are used to estimate the relative extent of calcite recrystallization in samples from four time points (core tops, 5.6, 9.4, and 37.1 Ma) at eight Ocean Drilling Program sites in the equatorial Atlantic (Ceara Rise) and equatorial Pacific (Ontong Java Plateau and two eastern equatorial Pacific sites). The possibility that site-to-site differences in calcite Sr/Ca at a given time point originated from temporal variations in ocean chemistry was eliminated by careful age control of samples for each time point, with sample ages differing by less than the oceanic residence times of Sr and Ca. The Sr/Ca and d18O values of 5.6- and 9.4-Ma samples from the less-carbonate-rich eastern equatorial Pacific sites and Ceara Rise Site 929 appear to be less diagenetically altered than the Sr/Ca and d18O values of contemporaneous samples from the more carbonate-rich sites. It is evident from these data that both Sr/Ca and d18O in bulk calcite have been diagenetically altered in some samples 5.6 Ma and older. These data indicate that noncarbonate sedimentary components, like clay and biogenic silica, have partially suppressed recrystallization at the lower carbonate sites. Sr/Ca data from the less altered, carbonate-poor sites indicate higher oceanic Sr/Ca relative to today at 5.6 and 9.4 Ma.

(Table S1) Stable carbon and oxygen isotopes and Mg/Ca ratios of planktonic foraminifera from ODP Hole 198-1209B

The Paleocene-Eocene Thermal Maximum (PETM) has been attributed to a rapid rise in greenhouse gas levels. If so, warming should have occurred at all latitudes, although amplified toward the poles. Existing records reveal an increase in high-latitude sea surface temperatures (SSTs) (8° to 10°C) and in bottom water temperatures (4° to 5°C). To date, however, the character of the tropical SST response during this event remains unconstrained. Here we address this deficiency by using paired oxygen isotope and minor element (magnesium/calcium) ratios of planktonic foraminifera from a tropical Pacific core to estimate changes in SST. Using mixed-layer foraminifera, we found that the combined proxies imply a 4° to 5°C rise in Pacific SST during the PETM. These results would necessitate a rise in atmospheric pCO2 to levels three to four times as high as those estimated for the late Paleocene.

Water temperature reconstructions based on paired Uk'37 and Tex86 records, and paired surface and subsurface Mg/Ca records

This dataset contains the collection of available published paired Uk'37 and Tex86 records spanning multi-millennial to multi-million year time scales, as well as a collection of Mg/Ca-derived temperatures measured in parallel on surface and subsurface dwelling foraminifera, both used in the analyses of Ho and Laepple, Nature Geoscience 2016. As the signal-to-noise ratios of proxy-derived Holocene temperatures are relatively low, we selected records that contain at least the last deglaciation (oldest sample >18kyr BP).

Comparison of Ba/Ca and d18OWATER as freshwater proxies: a multi-species core-top study on planktonic foraminifera from the vicinity of the Orinoco River mouth

Past river run-off is an important measure for the continental hydrological cycle and the as-sessment of freshwater input into the ocean. However, paleosalinity reconstructions applying different proxies in parallel often show offsets between the respective methods. Here, we compare the established foraminiferal Ba/Ca and d18OWATER salinity proxies for their capability to record the highly seasonal Orinoco freshwater plume in the eastern Caribbean. For this purpose we obtained a data set comprising Ba/Ca and d18OWATER determined on multiple spe-cies of planktonic foraminifera from core tops distributed around the Orinoco river mouth. Our findings indicate that interpretations based on either proxy could lead to different conclu-sions. In particular, Ba/Ca and d18OWATER diverge in their spatial distribution due to different governing factors. Apparently, the Orinoco freshwater plume is best tracked by Ba/Ca ratios of G. ruber (pink and sensu lato morphotypes), while d18OWATER based on the same species is more related to the local precipitation-evaporation balance overprinting the riverine freshwater contribution. Other shallow dwelling species (G. sacculifer, O. universa) show a muted response to the freshwater discharge, most likely due to their ecological and habitat prefer-ences. Extremely high Ba/Ca ratios recorded by G. ruber are attributed to Ba2+-desorption from suspended matter derived from the Orinoco. Samples taken most proximal to the freshwater source do not show pronounced Ba/Ca or d18OWATER anomalies. Here, the suspension loaded freshwater lid developing during maximum discharge suppresses foraminiferal populations. Both proxies are therefore biased towards dry season conditions at these sites, when surface salinity is only minimally reduced.