The amplitude of climatic change, as recorded in the benthic oxygen isotope record, has varied throughout geological time. During the late Pleistocene, changes in the atmospheric concentration of ...carbon dioxide (CO2) are an important control on this amplitude of variability. The contribution of CO2 to climate variability during the pre‐Quaternary however is unknown. Here we present a new boron isotope‐based CO2 record for the transition into the middle Miocene Climatic Optimum (MCO) between 15.5 and 17 Myr that shows pronounced variability between 300 ppm and 500 ppm on a roughly 100 kyr time scale during the MCO. The CO2 changes reconstructed for the Miocene are ~2 times larger in absolute terms (300 to 500 ppm compared to 180 to 280 ppm) than those associated with the late Pleistocene and ~15% larger in terms of climate forcing. In contrast, however, variability in the contemporaneous benthic oxygen isotope record (at ~1‰) is approximately two thirds the amplitude of that seen during the late Pleistocene. These observations indicate a lower overall sensitivity to CO2 forcing for Miocene (Antarctic only) ice sheets than their late Pleistocene (Antarctic plus lower latitude northern hemisphere) counterparts. When our Miocene CO2 record is compared to the estimated changes in contemporaneous δ18Osw (ice volume), they point to the existence of two reservoirs of ice on Antarctica. One of these reservoirs appears stable, while a second reservoir shows a level of dynamism that contradicts the results of coupled climate‐ice sheet model experiments given the CO2 concentrations that we reconstruct.
Key Points
The middle Miocene is characterized by CO2 variability between 300 and 500 ppmThe high‐amplitude CO2 variability is matched by the changes in the paleorecordsTwo regimes of ice volume‐CO2 variability identified in middle Miocene
Amorphous calcium carbonate (ACC) has been identified or inferred to exist in many groups of marine organisms that produce biominerals widely used as geochemical archives (e.g. foraminifera, ...molluscs, echinoderms). However, little is known about trace element incorporation into ACC, and thus it is not understood how precipitation through an ACC precursor might impact the fidelity of climate proxies and biomineralisation models built on the skeletal geochemistry of these marine calcifiers. To address this, we investigated the incorporation of Li, B, Na, Mg, Mn, Sr, Ba, and U into inorganic amorphous calcium magnesium carbonates precipitated from seawater under a variety of different carbonate chemistries, Mg/Ca ratios, and in the presence of aspartic and glutamic acid, two of the most common intracrystalline amino acids found in foraminifera and corals. ACC is highly enriched in most of these trace elements relative to the crystalline carbonates yet similar in some respects in terms of the factors influencing trace element partitioning. For example, ACC B/Ca is sensitive to the carbonate system, whilst Mg/Ca and Sr/Ca are largely a function of their respective ratio in seawater. In general, we find that most of the variance in the distribution coefficients of the other trace elements can be explained by some combination of the seawater carbonate chemistry and the seawater or ACC Mg/Ca ratio.
Boron isotope ratios, as measured in planktic foraminifera, can be a useful tracer of past ocean pH, and hence help to discern the concentration of CO2 in the ancient atmosphere. However, different ...species of planktic foraminifera demonstrate different patterns of boron isotope variation with ambient seawater pH. Therefore when applying the proxy to questions in the geological past, species-specific calibrations are preferable. Beyond the evolutionary history of a calibrated species, we must rely on our understanding of the causes of the observed “vital effects” in the modern ocean, and the applicability of that understanding to extinct species. Here we present a new open-ocean calibration of the planktic foraminifera Orbulina universa, measured via Multi-Collector Inductively Coupled Mass Spectrometry (MC-ICPMS). Unlike other symbiont-bearing foraminifera, O. universa record a δ11B (and hence pH) that is lower than its surrounding seawater, but with a pH-sensitivity roughly equal to that of aqueous borate ion. We discuss the significance of this for application of the boron isotope proxy in deep time, with recommendations for best practice and future research directions.
•A new, well-constrained boron isotope calibration for O. universa.•O. universa records lower pH than ambient seawater, which we suggest is due to living at depth.•We give recommendations for accounting for vital effects in extinct species.
The Middle Eocene Climatic Optimum (MECO) was a gradual warming event and carbon cycle perturbation that occurred between 40.5 and 40.1 Ma. A number of characteristics, including ...greater‐than‐expected deep‐sea carbonate dissolution, a lack of globally coherent negative δ13C excursion in marine carbonates, a duration longer than the characteristic timescale of carbon cycle recovery, and the absence of a clear trigger mechanism, challenge our current understanding of the Earth system and its regulatory feedbacks. This makes the MECO one of the most enigmatic events in the Cenozoic, dubbed a middle Eocene “carbon cycle conundrum.” Here we use boron isotopes in planktic foraminifera to better constrain pCO2 changes over the event. Over the MECO itself, we find that pCO2 rose by only 0.55–0.75 doublings, thus requiring a much more modest carbon injection than previously indicated by the alkenone δ13C‐pCO2 proxy. In addition, this rise in pCO2 was focused around the peak of the 400 kyr warming trend. Before this, considerable global carbonate δ18O change was asynchronous with any coherent ocean pH (and hence pCO2) excursion. This finding suggests that middle Eocene climate (and perhaps a nascent cryosphere) was highly sensitive to small changes in radiative forcing.
Plain Language Summary
Geoscientists often look to periods of global warming in the geological past to understand how the Earth responds to input of atmospheric CO2. However, during the Middle Eocene Climatic Optimum (or MECO) 40 million years ago, the Earth did not respond in the way one would expect, given what we know from these earlier warming events. The MECO poses a number of puzzles for geoscientists relating to what caused it and why the Earth system responded in the way it did. Before we can hope to answer these questions, however, we need to know what atmospheric CO2 levels were in the middle Eocene and how much they changed over the MECO event. Here we use boron isotope ratios in fossil plankton shells to tell us how ocean pH (which predominantly reflects CO2 levels) changed over the MECO. We show that relatively little change in CO2 at this time were associated with large‐scale changes in climate. This suggests that during the Eocene, when CO2 levels were similar to those likely to be reached by the end of this century, the Earth's climate (and possibly ice sheets) was very sensitive to minor disturbances.
Key Points
We present a new record of pCO2 across the MECO, from boron isotopes in foraminifera from multiple ocean drilling sites
Incorporating carbon cycle modeling, our data indicate pCO2 rise of about two thirds of a doubling across the event
pCO2 change during the MECO onset warming was limited, indicating heightened climate sensitivity or a nonthermal component to δ18O change
Paleoclimate records suggest that a rapid major transient Antarctic glaciation occurred across the Oligocene‐Miocene transition (OMT; ca. 23 Ma; ~50‐m sea level equivalent in 200–300 kyr). Orbital ...forcing has long been cited as an important factor determining the timing of the OMT glacial event. A similar orbital configuration occurred 1.2 Myr prior to the OMT, however, and was not associated with a major climate event, suggesting that additional mechanisms play an important role in ice sheet growth and decay. To improve our understanding of the OMT, we present a boron isotope‐based CO2 record between 22 and 24 Ma. This new record shows that δ11B/CO2 was comparatively stable in the million years prior to the OMT glaciation and decreased by 0.7‰ (equivalent to a CO2 increase of ~65 ppm) over ~300 kyr during the subsequent deglaciation. More data are needed, but we propose that the OMT glaciation was triggered by the same forces that initiated sustained Antarctic glaciation at the Eocene‐Oligocene transition: long‐term decline in CO2 to a critical threshold and a superimposed orbital configuration favorable to glaciation (an eccentricity minimum and low‐amplitude obliquity change). When comparing the reconstructed CO2 increase with estimates of δ18Osw during the deglaciation phase of the OMT, we find that the sensitivity of the cryosphere to CO2 forcing is consistent with recent ice sheet modeling studies that incorporate retreat into subglacial basins via ice cliff collapse with modest CO2 increase, with clear implications for future sea level rise.
Key Points
CO2 levels were relatively low (~265 ppm;
2σ−111+166 ppm) and comparatively stable in the 500 kyr prior to and during the glaciation
CO2 increased by ~65 ppm during the OMT deglaciation consistent with the latest generation of ice sheet models
The timing of the OMT glaciation is most likely controlled by both changes in CO2 and favorable orbital forcing
The boron isotopic ratio of
11
B/
10
B (δ
11
B
SRM951
) and trace element composition of marine carbonates are key proxies for understanding carbon cycling (pH) and palaeoceanographic change. ...However, method validation and comparability of results between laboratories requires carbonate reference materials. Here, we report results of an inter‐laboratory comparison study to both assign δ
11
B
SRM951
and trace element compositions to new synthetic marine carbonate reference materials (RMs), NIST RM 8301 (Coral) and NIST RM 8301 (Foram) and to assess the variance of data among laboratories. Non‐certified reference values and expanded 95% uncertainties for δ
11
B
SRM951
in NIST RM 8301 (Coral) (+24.17‰ ± 0.18‰) and NIST RM 8301 (Foram) (+14.51‰ ± 0.17‰) solutions were assigned by consensus approach using inter‐laboratory data. Differences reported among laboratories were considerably smaller than some previous inter‐laboratory comparisons, yet discrepancies could still lead to large differences in calculated seawater pH. Similarly, variability in reported trace element information among laboratories (e.g., Mg/Ca ± 5% RSD) was often greater than within a single laboratory (e.g., Mg/Ca < 2%). Such differences potentially alter proxy‐reconstructed seawater temperature by more than 2 °C. These now well‐characterised solutions are useful reference materials to help the palaeoceanographic community build a comprehensive view of past ocean changes.
The boron isotopic ratio of 11B/10B (δ11BSRM951) and trace element composition of marine carbonates are key proxies for understanding carbon cycling (pH) and palaeoceanographic change. However, ...method validation and comparability of results between laboratories requires carbonate reference materials. Here, we report results of an inter‐laboratory comparison study to both assign δ11BSRM951 and trace element compositions to new synthetic marine carbonate reference materials (RMs), NIST RM 8301 (Coral) and NIST RM 8301 (Foram) and to assess the variance of data among laboratories. Non‐certified reference values and expanded 95% uncertainties for δ11BSRM951 in NIST RM 8301 (Coral) (+24.17‰ ± 0.18‰) and NIST RM 8301 (Foram) (+14.51‰ ± 0.17‰) solutions were assigned by consensus approach using inter‐laboratory data. Differences reported among laboratories were considerably smaller than some previous inter‐laboratory comparisons, yet discrepancies could still lead to large differences in calculated seawater pH. Similarly, variability in reported trace element information among laboratories (e.g., Mg/Ca ± 5% RSD) was often greater than within a single laboratory (e.g., Mg/Ca < 2%). Such differences potentially alter proxy‐reconstructed seawater temperature by more than 2 °C. These now well‐characterised solutions are useful reference materials to help the palaeoceanographic community build a comprehensive view of past ocean changes.
Key Points
Interlaboratory consensus δ11B values for respectively NIST RM 8301 (Coral) and (Foram): +24.17±0.18‰ and +14.51±0.17‰.
Consensus trace element ratios (µmol mol−1) for respectively (Coral) and (Foram): Li/Ca = 5.40, 9.01; B/Ca = 528.1, 138.9; Mg/Ca 4.11 × 103, 2.62 × 103; Sr/Ca 8.10 × 103, 1.34 × 103; Cd/Ca 0.20, 0.58; Ba/Ca 5.92, 3.90; U/Ca 0.829, 0.069.
Identifying processes within the Earth System that have modulated atmospheric pCO2 during each glacial cycle of the late Pleistocene stands as one of the grand challenges in climate science. The ...growing array of surface ocean pH estimates from the boron isotope proxy across the last glacial termination may reveal regions of the ocean that influenced the timing and magnitude of pCO2 rise. Here we present two new boron isotope records from the subtropical‐subpolar transition zone of the Southwest Pacific that span the last 20 kyr, as well as new radiocarbon data from the same cores. The new data suggest this region was a source of carbon to the atmosphere rather than a moderate sink as it is today. Significantly higher outgassing is observed between ~16.5 and 14 kyr BP, associated with increasing δ13C and CO32− at depth, suggesting loss of carbon from the intermediate ocean to the atmosphere. We use these new boron isotope records together with existing records to build a composite pH/pCO2 curve for the surface oceans. The pH disequilibrium/CO2 outgassing was widespread throughout the last deglaciation, likely explained by upwelling of CO2 from the deep/intermediate ocean. During the Holocene, a smaller outgassing peak is observed at a time of relatively stable atmospheric CO2, which may be explained by regrowth of the terrestrial biosphere countering ocean CO2 release. Our stack is likely biased toward upwelling/CO2 source regions. Nevertheless, the composite pCO2 curve provides robust evidence that various parts of the ocean were releasing CO2 to the atmosphere over the last 25 kyr.
Key Points
Boron‐isotope‐based pH reconstructions indicate that the subtropical/subpolar Southwest Pacific was a source of CO2 during the last 19 ka
Major CO2 outgassing from the Southwest Pacific was associated with enhanced ventilation of intermediate waters between 16.5 and 14 kyr BP
A surface pH/pCO2 composite derived from 12 planktic δ11B records shows widespread CO2 release from the ocean during the last deglaciation
Abstract The Middle Eocene Climatic Optimum (MECO) was a gradual warming event and carbon cycle perturbation that occurred between 40.5 and 40.1 Ma. A number of characteristics, including ...greater‐than‐expected deep‐sea carbonate dissolution, a lack of globally coherent negative δ 13 C excursion in marine carbonates, a duration longer than the characteristic timescale of carbon cycle recovery, and the absence of a clear trigger mechanism, challenge our current understanding of the Earth system and its regulatory feedbacks. This makes the MECO one of the most enigmatic events in the Cenozoic, dubbed a middle Eocene “carbon cycle conundrum.” Here we use boron isotopes in planktic foraminifera to better constrain pCO 2 changes over the event. Over the MECO itself, we find that pCO 2 rose by only 0.55–0.75 doublings, thus requiring a much more modest carbon injection than previously indicated by the alkenone δ 13 C‐pCO 2 proxy. In addition, this rise in pCO 2 was focused around the peak of the 400 kyr warming trend. Before this, considerable global carbonate δ 18 O change was asynchronous with any coherent ocean pH (and hence pCO 2 ) excursion. This finding suggests that middle Eocene climate (and perhaps a nascent cryosphere) was highly sensitive to small changes in radiative forcing.
Plain Language Summary Geoscientists often look to periods of global warming in the geological past to understand how the Earth responds to input of atmospheric CO 2 . However, during the Middle Eocene Climatic Optimum (or MECO) 40 million years ago, the Earth did not respond in the way one would expect, given what we know from these earlier warming events. The MECO poses a number of puzzles for geoscientists relating to what caused it and why the Earth system responded in the way it did. Before we can hope to answer these questions, however, we need to know what atmospheric CO 2 levels were in the middle Eocene and how much they changed over the MECO event. Here we use boron isotope ratios in fossil plankton shells to tell us how ocean pH (which predominantly reflects CO 2 levels) changed over the MECO. We show that relatively little change in CO 2 at this time were associated with large‐scale changes in climate. This suggests that during the Eocene, when CO 2 levels were similar to those likely to be reached by the end of this century, the Earth's climate (and possibly ice sheets) was very sensitive to minor disturbances.
Key Points We present a new record of pCO 2 across the MECO, from boron isotopes in foraminifera from multiple ocean drilling sites Incorporating carbon cycle modeling, our data indicate pCO 2 rise of about two thirds of a doubling across the event pCO 2 change during the MECO onset warming was limited, indicating heightened climate sensitivity or a nonthermal component to δ 18 O change
The boron isotope composition (δ11B) of foraminiferal calcite reflects the pH and the boron isotope composition of the seawater the foraminifer grew in. For pH reconstructions, the δ11B of seawater ...must therefore be known, but information on this parameter is limited. Here we reconstruct Neogene seawater δ11B based on the δ11B difference between paired measurements of planktic and benthic foraminifera and an estimate of the coeval water column pH gradient from their δ13C values. Carbon cycle model simulations underscore that the ΔpH–Δδ13C relationship is relatively insensitive to ocean and carbon cycle changes, validating our approach. Our reconstructions suggest that δ11Bsw was ∼ 37.5 ‰ during the early and middle Miocene (roughly 23–12 Ma) and rapidly increased during the late Miocene (between 12 and 5 Ma) towards the modern value of 39.61 ‰. Strikingly, this pattern is similar to the evolution of the seawater isotope composition of Mg, Li and Ca, suggesting a common forcing mechanism. Based on the observed direction of change, we hypothesize that an increase in secondary mineral formation during continental weathering affected the isotope composition of riverine input to the ocean since 14 Ma.
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