Early Pleistocene Obliquity‐Scale pCO2 Variability at ~1.5 Million Years Ago

In the early Pleistocene, global temperature cycles predominantly varied with ~41‐kyr (obliquity‐scale) periodicity. Atmospheric greenhouse gas concentrations likely played a role in these climate cycles; marine sediments provide an indirect geochemical means to estimate early Pleistocene CO2. Here we present a boron isotope‐based record of continuous high‐resolution surface ocean pH and inferred atmospheric CO2 changes. Our results show that, within a window of time in the early Pleistocene (1.38–1.54 Ma), pCO2 varied with obliquity, confirming that, analogous to late Pleistocene conditions, the carbon cycle and climate covaried at ~1.5 Ma. Pairing the reconstructed early Pleistocene pCO2 amplitude (92 ± 13 μatm) with a comparably smaller global surface temperature glacial/interglacial amplitude (3.0 ± 0.5 K) yields a surface temperature change to CO2 radiative forcing ratio of S[CO2]~0.75 (±0.5) °C−1·W−1·m−2, as compared to the late Pleistocene S[CO2] value of ~1.75 (±0.6) °C−1·W−1·m−2. This direct comparison of pCO2 and temperature implicitly incorporates the large ice sheet forcing as an internal feedback and is not directly applicable to future warming. We evaluate this result with a simple climate model and show that the presumably thinner, though extensive, northern hemisphere ice sheets would increase surface temperature sensitivity to radiative forcing. Thus, the mechanism to dampen actual temperature variability in the early Pleistocene more likely lies with Southern Ocean circulation dynamics or antiphase hemispheric forcing. We also compile this new carbon dioxide record with published Plio‐Pleistocene δ11B records using consistent boundary conditions and explore potential reasons for the discrepancy between Pliocene pCO2 based on different planktic foraminifera.Key PointsEarly Pleistocene pCO2 roughly varied with obliquity cyclesInterglacial pCO2 was similar in the early and late Pleistocene; glacial pCO2 declined over the mid‐Pleistocene transitionDiscrepancies between δ11B values and corresponding pCO2 estimates from G. ruber and T. sacculifer are observed and may indicate evolving vital effectsPeer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/147130/1/palo20675-sup-0004-2018PA003349-S03.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/147130/2/palo20675.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/147130/3/palo20675-sup-0002-2018PA003349-S01.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/147130/4/palo20675_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/147130/5/palo20675-sup-0005-2018PA003349-S04.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/147130/6/palo20675-sup-0003-2018PA003349-S02.pd

Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation

Plankton, corals, and other organisms produce calcium carbonate skeletons that are integral to their survival, form a key component of the global carbon cycle, and record an archive of past oceanographic conditions in their geochemistry. A key aspect of the formation of these biominerals is the interaction between organic templating structures and mineral precipitation processes. Laboratory-based studies have shown that these atomic-scale processes can profoundly influence the architecture and composition of minerals, but their importance in calcifying organisms is poorly understood because it is difficult to measure the chemistry of in vivo biomineral interfaces at spatially relevant scales. Understanding the role of templates in biomineral nucleation, and their importance in skeletal geochemistry requires an integrated, multiscale approach, which can place atom-scale observations of organic-mineral interfaces within a broader structural and geochemical context. Here we map the chemistry of an embedded organic template structure within a carbonate skeleton of the foraminifera Orbulina universa using both atom probe tomography (APT), a 3D chemical imaging technique with Angström-level spatial resolution, and time-of-flight secondary ionization mass spectrometry (ToF-SIMS), a 2D chemical imaging technique with submicron resolution. We quantitatively link these observations, revealing that the organic template in O. universa is uniquely enriched in both Na andMg, and contributes to intraskeletal chemical heterogeneity. Our APT analyses reveal the cation composition of the organic surface, offering evidence to suggest that cations other than Ca2+, previously considered passive spectator ions in biomineral templating, may be important in defining the energetics of carbonate nucleation on organic template

Ventilation history of Nordic Seas overflows during the last (de)glacial period revealed by species-specific benthic foraminiferal 14 C dates

Formation of deep water in the high-latitude North Atlantic is important for the global meridional ocean circulation, and its variability in the past may have played an important role in regional and global climate change. Here we study ocean circulation associated with the last (de)glacial period, using water-column radiocarbon age reconstructions in the Faroe-Shetland Channel, southeastern Norwegian Sea, and from the Iceland Basin, central North Atlantic. The presence of tephra layer Faroe Marine Ash Zone II, dated to ~26.7 ka, enables us to determine that the middepth (1179 m water depth) and shallow subsurface reservoir ages were ~1500 and 1100 14C years, respectively, older during the late glacial period compared to modern, suggesting substantial suppression of the overturning circulation in the Nordic Seas. During the late Last Glacial Maximum and the onset of deglaciation (~20–18 ka), Nordic Seas overflow was weak but active. During the early deglaciation (~17.5–14.5 ka), our data reveal large differences between 14C ventilation ages that are derived from dating different benthic foraminiferal species: Pyrgo and other miliolid species yield ventilation ages >6000 14C years, while all other species reveal ventilation ages <2000 14C years. These data either suggest subcentennial, regional, circulation changes or that miliolid-based 14C ages are biased due to taphonomic or vital processes. Implications of each interpretation are discussed. Regardless of this “enigma,” the onset of the Bølling-Allerød interstadial (14.5 ka) is clearly marked by an increase in middepth Nordic Seas ventilation and the renewal of a stronger overflow

Calibration of the B/Ca proxy in the planktic foraminifer Orbulina universa to Paleocene seawater conditions

This research is funded by NSF [OCE12-32987] to BH.The B/Ca ratio of planktic foraminiferal calcite, a proxy for the surface ocean carbonate system, displays large negative excursions during the Paleocene-Eocene Thermal Maximum (PETM, 55.9 Ma), consistent with rapid ocean acidification at that time. However, the B/Ca excursion measured at the PETM exceeds a magnitude that modern pH-calibrations can explain. Numerous other controls on the proxy have been suggested, including foraminiferal growth rate and the total concentration of Dissolved Inorganic Carbon (DIC). Here we present new calibrations for B/Ca vs. the combined effects of pH and DIC in the symbiont-bearing planktic foraminifer Orbulina universa, grown in culture solutions with simulated Paleocene seawater elemental composition (high [Ca], low [Mg], and low [B]T). We also investigate the isolated effects of low seawater total boron concentration ([B]T), high [Ca], reduced symbiont photosynthetic activity, and average shell growth rate on O. universa B/Ca in order to further understand the proxy systematics and to determine other possible influences on the PETM records. We find that average shell growth rate does not appear to determine B/Ca in high calcite saturation experiments. In addition, our “Paleocene” calibration shows higher sensitivity than the modern calibration at low [B(OH)4-]/DIC. Given a large DIC pulse at the PETM, this amplification of the B/Ca response can more fully explain the PETM B/Ca excursion. However, further calibrations with other foraminifer species are needed to determine the range of foraminifer species-specific proxy sensitivities under these conditions for quantitative reconstruction of large carbon cycle perturbations.Publisher PDFPeer reviewe

Stabile Isotopen- und Spurenelementzusammensetzung von Foraminiferenschalen - vom Einbau bis zur Lösung

The ocean is the most important reservoir for the greenhouse gas CO2 and in order to understand the natural variability in the atmospheric concentration, we have to understand the storage capacity of the ocean over past timescales. To reconstruct the physicochemical conditions of the past, measurable recorders ( proxies ) have to be applied in order to estimate conditions which can no longer be observed. With regard to marine carbonate chemistry, a number of biogeochemical proxy-relationships have been proposed and established. Many of them rely on the chemical composition of calcareous skeletal remains such as foraminifera shells. However, problems in application and reliability of these proxies may arise from uncertainties in the incorporation behaviour and their potential instability in the geological archive. While physiological processes of the foraminifera and associated organisms are known to alter a number of proxy relationships, several proxy records are known or suspected to be modified by partial dissolution in the sediment. To investigate whether boron isotopes (pH-proxy) and Ba/Ca (proxy for the oceanwide distribution of alkalinity) in foraminiferal shells are affected by biological activity, culture experiments with living animals have been carried out. While symbiont photosynthesis causes the d11B/pH-record to deviate from the surrounding seawater-pH, Ba/Ca proved to be unaffected by changing alkalinity.Laboratory experiments were designed to investigate the effect of carbonate dissolution on foraminiferal shell chemistry. Comparison of various chemical proxies demonstrates that the dissolution behaviour is poorly understood. Similarly, evidence from culture experiments suggests that the use of foraminiferal shell weight to determine bottomwater-[CO32-] is much more complicated than so far assumed.The dissertation provides detailed descriptions of theexperimental methods and discusses the meaning of the results for paleoreconstructions

(Table 1, 2) Foraminifera biometric data, and boron isotopic composition of Globigerinoides sacculifer of sediments from the Ontong-Java Plateau

Sediment samples from the Ontong-Java Plateau in the Pacific and the 90° east ridge in the Indian Ocean were used to investigate whether shell size and early diagenesis affect d11B of the symbiont-bearing planktonic foraminifer Globigerinoides sacculifer. In pristine shells from both study locations we found a systematic increase of d11B and Mg/Ca with shell size. Shells in the sieve size class 515–865 µm revealed d11B values +2.1 to +2.3 per mil higher than shells in the 250–380 µm class. This pattern is most likely due to differences in symbiont photosynthetic activity and its integrated effect on the pH of the foraminiferal microenvironment. We therefore suggest smaller individuals must live at approximately 50–100 m water depth where ambient light levels are lower. Using the empirical calibration curve for d11B in G. sacculifer, only shells larger than 425 µm reflect surface seawater pH. Partial dissolution of shells derived from deeper sediment cores was determined by shell weight analyses and investigation of the shell surface microstructure by scanning electron microscopy. The d11B in partially dissolved shells is up to 2 per mil lower relative to pristine shells of the same size class. In agreement with a relatively higher weight loss in smaller shells, samples from the Ontong-Java Plateau show a more pronounced dissolution effect than larger shells. On the basis of the primary size effect and potential postdepositional dissolution effects, we recommend the use of shells that are visually pristine and, in the case of G. sacculifer, larger than 500 μm for paleoreconstructions

B-isotope and Mg/Ca ratios of planktonic foraminifera from ODP Hole 108-668B and esimates of salinity, alkalinity and pCO2 (Table 1)

Knowledge of past atmospheric pCO2 is important for evaluating the role of greenhouse gases in climate forcing. Ice core records show the tight correlation between climate change and pCO2, but records are limited to the past ~900 kyr. We present surface ocean pH and pCO2 data, reconstructed from boron isotopes in planktonic foraminifera over two full glacial cycles (0-140 and 300-420 kyr). The data co-vary strongly with the Vostok pCO2-record and demonstrate that the coupling between surface ocean chemistry and the atmosphere is recorded in marine archives, allowing for quantitative estimation of atmospheric pCO2 beyond the reach of ice cores

The use of Mg/Ca as a seawater temerature proxy

The underlying basis for Mg/Ca paleothermometry is that the amount of magnesium in calcite precipitated from seawater is dependent on temperature. Here we review the state of the art of the Mg/Ca seawater paleotemperature proxy, summarized by the following: 1) Calcite, whether formed abiotically or biologically as foraminifera and ostracode shells, incörporates variable amounts of magnesium into the crystal structure. 2) Uptake of Mg varies positively with temperature. 3) The relationship between temperature and the amount of Mg in calcite has been quantified by experiments on synthetic calcite growth and by culture, core top, and sediment trap experiments using living organisms. 4) The most careful calibrations of the Mg/Ca paleothermometer have been done for planktic foraminifera, then benthic foraminifera; there are species-specific variations in the amount of Mg incorporated into foraminifera shells. 5) The Mg/Ca ratio of calcite from planktic foraminifera in deep-sea cores has been widely used to interpret sea surface temperatures. 6) Measurement of both Mg/Ca and δ18O in planktic foraminifera have been used to calculate δ18O in seawater, and after correction for global ice volume, salinity could be inferred. 7) Mg/Ca from benthic foraminifera have been used to reconstruct deep-sea temperatures and cooling of ~12°C over the last 50 million years. 8) One problem with the Mg/Ca seawater temperature proxy is partial dissolution of. foraminifer shells, which lowers the Mg/Ca, and leads to an underestimation of ocean temperature. Benthic foraminifers appear to be more resistant to partial dissolution. 9) Past changes in the Mg/Ca ratio of seawater are an important factor in determining the amount of Mg in fossil skeletal calcite, and thus add another variable to the Mg/Ca temperature proxy. All Mg/Ca paleotemperature studies on fossil calcite older than Pleistocene should take into account the Mg/Ca of the seawater from which it precipitated