Millennial-scale surface and subsurface paleothermometry from the northeast Atlantic, 55-8 ka BP

We present high-resolution records of upper ocean temperatures derived from Mg/Ca ratios of surface-dwelling Globigerina bulloides and subsurface-dwelling Neogloboquadrina pachyderma sinistral and the relative abundance of N. pachyderma sinistral for the period 55-8 ka BP from NE Atlantic sediment core MD01-2461. Millennial-scale temporal variability and longer-term trends in these records enable us to develop a detailed picture of past ocean conditions such as a weakening of thermocline intensity from marine isotope stage 3 (MIS 3) to the last glacial maximum (LGM). The correspondence of all temperature proxies and convergence of paired oxygen isotope (δ18O) records from both planktonic species implies a breakdown in the thermocline and year-round mixing of the upper water column through the LGM, perhaps related to decreasing insolation and additional cooling in association with the expansion of the circum-North Atlantic ice sheets. Millennial-scale divergence in surface and subsurface temperatures and δ18O across the last glacial correspond to meltwater release and the development of a strong halocline associated with both Heinrich (H) events and instabilities of the NW European ice sheet. During such episodes, G. bulloides Mg/Ca appears to record ambient, even warming summer sea surface temperatures across H events while the other proxies record maximum cooling

Investigating the effects of growth rate and temperature on the B/Ca ratio and δ11B during inorganic calcite formation

To deconvolve the effect of growth rate and temperature on the boron partitioning into calcite and its isotope fractionation, seeded calcite precipitation experiments were performed at a constant temperature and various growth rates and at a constant growth rate and various temperatures. We show that boron partitioning increases with increasing growth rate and decreases with increasing temperature. The B isotope fractionation between calcite and B(OH)4− increases with increasing growth rate favoring the lighter B isotope for incorporation into calcite whereas no effect of temperature was observed within the temperature range investigated (12 °C to 32 °C). At the lowest temperature and growth rate δ11B of the calcite almost equals that of B(OH)4− in solution. Applying the surface entrapment model (SEMO) of Watson and Liang (1995) to our data, we demonstrate that the observed effects of temperature and growth rate on B concentration can be explained by processes in the near surface layer of the calcite crystal

Calcite saturation, foraminiferal test mass, and Mg/Ca-based temperatures dissolution corrected using XDX—A 150 ka record from the western Indian Ocean

A record of deep-sea calcite saturation inline image, derived from X-ray computed tomography-based foraminifer dissolution index, XDX, was constructed for the past 150 ka for a core from the deep (4157 m) tropical western Indian Ocean. G. sacculifer and N. dutertrei recorded a similar dissolution history, consistent with the process of calcite compensation. Peaks in calcite saturation (∼15 µmol/kg higher than the present-day value) occurred during deglaciations and early in MIS 3. Dissolution maxima coincided with transitions to colder stages. The mass record of G. sacculifer better indicated preservation than did that of N. dutertrei or G. ruber. Dissolution-corrected Mg/Ca-derived SST records, like other SST records from marginal Indian Ocean sites, showed coolest temperatures of the last 150 ka in early MIS 3, when mixed layer temperatures were ∼4°C lower than present SST. Temperatures recorded by N. dutertrei showed the thermocline to be ∼4°C colder in MIS 3 compared to the Holocene (8 ka B.P.)

Calibration of Mg/Ca thermometry in planktonic foraminifera from a sediment trap time series

Paired Mg/Ca and δ18O measurements on planktonic foraminiferal species (G. ruber white, G. ruber pink, G. sacculifer, G. conglobatus, G. aequilateralis, O. universa, N. dutertrei, P. obliquiloculata, G. inflata, G. truncatulinoides, G. hirsuta, and G. crassaformis) from a 6-year sediment trap time series in the Sargasso Sea were used to define the sensitivity of foraminiferal Mg/Ca to calcification temperature. Habitat depths and calcification temperatures were estimated from comparison of δ18O of foraminifera with equilibrium calcite, based on historical temperature and salinity data. When considered together, Mg/Ca (mmol/mol) of all species, except two, show a significant (r = 0.93) relationship with temperature (T °C) of the form Mg/Ca = 0.38 (±0.02) exp 0.090 (±0.003)T, equivalent to a 9.0 ± 0.3% change in Mg/Ca for a 1°C change in temperature. Small differences exist in calibrations between species and between different size fractions of the same species. O. universa and G. aequilateralis have higher Mg/Ca than other species, and in general, data can be best described with the same temperature sensitivity for all species and pre-exponential constants in the sequence O. universa > G. aequilateralis ≈ G. bulloides > G. ruber ≈ G. sacculifer ≈ other species. This approach gives an accuracy of ±1.2°C in the estimation of calcification temperature. The ∼9% sensitivity to temperature is similar to published studies from culture and core top calibrations, but differences exist from some literature values of pre-exponential constants. Different cleaning methodologies and artefacts of core top dissolution are probably implicated, and perhaps environmental factors yet understood. Planktonic foraminiferal Mg/Ca temperature estimates can be used for reconstructing surface temperatures and mixed and thermocline temperatures (using G. ruber pink, G. ruber white, G. sacculifer, N. dutertrei, P. obliquiloculata, etc.). The existence of a single Mg thermometry equation is valuable for extinct species, although use of species-specific equations will, where statistically significant, provide more accurate evaluation of Mg/Ca paleotemperature

High-precision determination of lithium and magnesium isotopes utilising single column separation and multi-collector inductively coupled plasma mass spectrometry

Li and Mg isotopes are increasingly used as a combined tool within the geosciences. However, established methods require separate sample purification protocols utilising several column separation procedures. This study presents a single-step cation-exchange method for quantitative separation of trace levels of Li and Mg from multiple sample matrices

Glacial-interglacial changes in bottom-water oxygen content on the Portuguese margin

During the last and penultimate glacial maxima, atmospheric CO2 concentrations were lower than present, possibly in part because of increased storage of respired carbon in the deep oceans. The amount of respired carbon present in a water mass can be calculated from its oxygen content through apparent oxygen utilization; the oxygen content can in turn be calculated from the carbon isotope gradient within the sediment column. Here we analyse the shells of benthic foraminifera occurring at the sediment surface and the oxic/anoxic interface on the Portuguese Margin to reconstruct the carbon isotope gradient and hence bottom-water oxygenation over the past 150,000 years. We find that bottom-water oxygen concentrations were 45 and 65 μmol kg−1 lower than present during the last and penultimate glacial maxima, respectively. We calculate that concentrations of remineralized organic carbon were at least twice as high as today during the glacial maxima. We attribute these changes to decreased ventilation linked to a reorganization of ocean circulation and a strengthened global biological pump. If the respired carbon pool was of a similar size throughout the entire glacial deep Atlantic basin, then this sink could account for 15 and 20 per cent of the glacial PCO2 drawdown during the last and penultimate glacial maxima

Controls on boron incorporation in cultured tests of the planktic foraminifer Orbulina universa

Culture experiments with living planktic foraminifers reveal that the ratio of boron to calcium (B/Ca) in Orbulina universa increases from 56 to 92 μmol mol−1 when pH is raised from 7.61+/–0.02 to 8.67+/–0.03 (total scale). Across this pH range, the abundances of carbonate, bicarbonate, and borate ions also change (+530, −500, and +170 μmol kg−1, respectively). Thus specific carbonate system control(s) on B/Ca remain unclear, complicating interpretation of paleorecords. B/Ca in cultured O. universa also increases with salinity (55–72 μmol mol−1 from 29.9–35.4‰) and seawater boron concentration (62–899 μmol mol−1 from 4–40 ppm B), suggesting that these parameters may need to be taken into account for paleorecords spanning large salinity changes (~ 2‰) and for samples grown in seawater whose boron concentration ([B]SW) differs from modern by more than 0.25 ppm. While our results are consistent with the predominant incorporation of the charged borate species B(OH)4−into foraminiferal calcite, the behavior of the partition coefficient KD (defined as [B/Ca]calcite/[B(OH)4−/HCO3−]seawater) cannot be explained by borate incorporation alone, and suggests the involvement of other pH-sensitive ions such as CO3 2− For a given increase in seawater B(OH)4−, the corresponding increase in B/Ca is stronger when B(OH)4− is raised by increasing [B]SW than when it is raised by increasing pH. These results suggest that B incorporation controls should be reconsidered. Additional insight is gained from laser-ablation ICP-MS profiles, which reveal variable B/Ca distributions within individual shells

Antarctic Intermediate Water properties since 400 ka recorded in infaunal (Uvigerina peregrina) and epifaunal (Planulina wuellerstorfi) benthic foraminifera

Reconstruction of intermediate water properties is important for understanding feedbacks within the ocean-climate system, particularly since these water masses are capable of driving high–low latitude teleconnections. Nevertheless, information about intermediate water mass evolution through the late Pleistocene remains limited. This paper examines changes in Antarctic Intermediate Water (AAIW), the most extensive intermediate water mass in the modern ocean through the last 400 kyr using the stable isotopic composition (δ18O and δ13C) and trace element concentration (Mg/Ca and B/Ca) of two benthic foraminiferal species from the same samples: epifaunal Planulina wuellerstorfi and infaunal Uvigerina peregrina. Our results confirm that the most reasonable estimates of AAIW temperature and Δ[CO2−3] are generated by Mg/CaU. peregrina and B/CaP. wuellerstorfi, respectively. We present a 400 kyr record of intermediate water temperature and Δ[CO2−3] from a sediment core from the Southwest Pacific (DSDP site 593; 40°30′S, 167°41′E, 1068 m water depth), which lies within the core of modern AAIW. Our results suggest that a combination of geochemical analyses on both infaunal and epifaunal benthic foraminiferal species yields important information about this critical water mass through the late Pleistocene. When combined with two nearby records of water properties from deeper depths, our data demonstrate that during interglacial stages of the late Pleistocene, AAIW and Circumpolar Deep Water (CPDW) have more similar water mass properties (temperature and δ13C), while glacial stages are typified by dissimilar properties between AAIW and CPDW in the Southwest Pacific. Our new Δ[CO2−3] record shows short time-scale variations, but a lack of coherent glacial–interglacial variability indicating that large quantities of carbon were not stored in intermediate waters during recent glacial periods

Evolution of South Atlantic density and chemical stratification across the last deglaciation.

Explanations of the glacial-interglacial variations in atmospheric pCO2 invoke a significant role for the deep ocean in the storage of CO2. Deep-ocean density stratification has been proposed as a mechanism to promote the storage of CO2 in the deep ocean during glacial times. A wealth of proxy data supports the presence of a "chemical divide" between intermediate and deep water in the glacial Atlantic Ocean, which indirectly points to an increase in deep-ocean density stratification. However, direct observational evidence of changes in the primary controls of ocean density stratification, i.e., temperature and salinity, remain scarce. Here, we use Mg/Ca-derived seawater temperature and salinity estimates determined from temperature-corrected δ(18)O measurements on the benthic foraminifer Uvigerina spp. from deep and intermediate water-depth marine sediment cores to reconstruct the changes in density of sub-Antarctic South Atlantic water masses over the last deglaciation (i.e., 22-2 ka before present). We find that a major breakdown in the physical density stratification significantly lags the breakdown of the deep-intermediate chemical divide, as indicated by the chemical tracers of benthic foraminifer δ(13)C and foraminifer/coral (14)C. Our results indicate that chemical destratification likely resulted in the first rise in atmospheric pCO2, whereas the density destratification of the deep South Atlantic lags the second rise in atmospheric pCO2 during the late deglacial period. Our findings emphasize that the physical and chemical destratification of the ocean are not as tightly coupled as generally assumed.We are grateful to I. Mather, J. Rolfe, F. Dewilde and G. Isguder for preparing and performing isotopic analyses, as well as C. Daunt, S. Souanef-Ureta and M. Greaves for technical assistance in performing trace element analysis. J.R. was funded jointly by the British Geological Survey/British Antarctic Survey (Natural Environment Research Council) and the University of Cambridge. J.G. was funded by the Gates Cambridge Trust. L.C.S. acknowledges support from the Royal Society and NERC grant NE/J010545/1. C.W. acknowledges support from the European Research Council grant ACCLIMATE/no 339108. This is LSCE contribution 5514. This work was funded (in part) by the European Research Council (ERC grant 2010-NEWLOG ADG-267931 HE). N.V.R. acknowledges support from EU RTN NICE (no. 36127). We thank the captain and crew of the RRS James Clark Ross for facilitating the collection of the marine sediment core GC528.This is the author accepted manuscript. The final version is available from PNAS via http://dx.doi.org/10.1073/pnas.151125211

High-precision determination of lithium and magnesium isotopes utilising single column separation and multi-collector inductively coupled plasma mass spectrometry.

RATIONALE: Li and Mg isotopes are increasingly used as a combined tool within the geosciences. However, established methods require separate sample purification protocols utilising several column separation procedures. This study presents a single-step cation-exchange method for quantitative separation of trace levels of Li and Mg from multiple sample matrices. METHODS: The column method utilises the macro-porous AGMP-50 resin and a high-aspect ratio column, allowing quantitative separation of Li and Mg from natural waters, sediments, rocks and carbonate matrices following the same elution protocol. High-precision isotope determination was conducted by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) on the Thermo Scientific™ NEPTUNE Plus™ fitted with 1013  Ω amplifiers which allow accurate and precise measurements at ion beams ≤0.51 V. RESULTS: Sub-nanogram Li samples (0.3-0.5 ng) were regularly separated (yielding Mg masses of 1-70 μg) using the presented column method. The total sample consumption during isotopic analysis is <0.5 ng Li and <115 ng Mg with long-term external 2σ precisions of ±0.39‰ for δ7 Li and ±0.07‰ for δ26 Mg. The results for geological reference standards and seawater analysed by our method are in excellent agreement with published values despite the order of magnitude lower sample consumption. CONCLUSIONS: The possibility of eluting small sample masses and the low analytical sample consumption make this method ideal for samples of limited mass or low Li concentration, such as foraminifera, mineral separates or dilute river waters