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1.
Nat Commun ; 14(1): 5432, 2023 Sep 05.
Article En | MEDLINE | ID: mdl-37669925

High-resolution ice core records from coastal Antarctica are particularly useful to inform our understanding of environmental changes and their drivers. Here, we present a decadally resolved record of sea-salt sodium (a proxy for open-ocean area) and non-sea salt calcium (a proxy for continental dust) from the well-dated Roosevelt Island Climate Evolution (RICE) core, focusing on the time period between 40-26 ka BP. The RICE dust record exhibits an abrupt shift towards a higher mean dust concentration at 32 ka BP. Investigating existing ice-core records, we find this shift is a prominent feature across Antarctica. We propose that this shift is linked to an equatorward displacement of Southern Hemisphere westerly winds. Subsequent to the wind shift, data suggest a weakening of Southern Ocean upwelling and a decline of atmospheric CO2 to lower glacial values, hence making this shift an important glacial climate event with potentially important insights for future projections.

2.
Nature ; 617(7959): 100-104, 2023 05.
Article En | MEDLINE | ID: mdl-37095266

During the last ice age, the Laurentide Ice Sheet exhibited extreme iceberg discharge events that are recorded in North Atlantic sediments1. These Heinrich events have far-reaching climate impacts, including widespread disruptions to hydrological and biogeochemical cycles2-4. They occurred during Heinrich stadials-cold periods with strongly weakened Atlantic overturning circulation5-7. Heinrich-type variability is not distinctive in Greenland water isotope ratios, a well-dated site temperature proxy8, complicating efforts to assess their regional climate impact and phasing against Antarctic climate change. Here we show that Heinrich events have no detectable temperature impact on Greenland and cooling occurs at the onset of several Heinrich stadials, and that both types of Heinrich variability have a distinct imprint on Antarctic climate. Antarctic ice cores show accelerated warming that is synchronous with increases in methane during Heinrich events, suggesting an atmospheric teleconnection9, despite the absence of a Greenland climate signal. Greenland ice-core nitrogen stable isotope ratios, a sensitive temperature proxy, indicate an abrupt cooling of about three degrees Celsius at the onset of Heinrich Stadial 1 (17.8 thousand years before present, where present is defined as 1950). Antarctic warming lags this cooling by 133 ± 93 years, consistent with an oceanic teleconnection. Paradoxically, proximal sites are less affected by Heinrich events than remote sites, suggesting spatially complex event dynamics.

3.
Proc Natl Acad Sci U S A ; 119(45): e2205545119, 2022 Nov 08.
Article En | MEDLINE | ID: mdl-36322740

Ice cores from the northwestern Tibetan Plateau (NWTP) contain long records of regional climate variability, but refrozen meltwater and dust in these cores has hampered development of robust timescales. Here, we introduce an approach to dating the ice via the isotopic composition of atmospheric O2 in air bubbles (δ18Oatm), along with annual layer counting and radiocarbon dating. We provide a robust chronology for water isotope records (δ18Oice and d-excess) from three ice cores from the Guliya ice cap in the NWTP. The measurement of δ18Oatm, although common in polar ice core timescales, has rarely been used on ice cores from low-latitude, high-altitude glaciers due to (1) low air pressure, (2) the common presence of refrozen melt that adds dissolved gases and reduces the amount of air available for analysis, and (3) the respiratory consumption of molecular oxygen (O2) by micro-organisms in the ice, which fractionates the δ18O of O2 from the atmospheric value. Here, we make corrections for melt and respiration to address these complications. The resulting records of water isotopes from the Guliya ice cores reveal climatic variations over the last 15,000 y, the timings of which correspond to those observed in independently dated lake and speleothem records and confirm that the Guliya ice cap existed before the Holocene. The millennial-scale drivers of δ18Oice are complex and temporally variable; however, Guliya δ18Oice values since the mid-20th century are the highest since the beginning of the Holocene and have increased with regional air temperature.


Ice Cover , Radiometric Dating , Tibet , Temperature , Isotopes , Water
4.
Nat Commun ; 13(1): 5867, 2022 Oct 04.
Article En | MEDLINE | ID: mdl-36195764

Our understanding of climate dynamics during millennial-scale events is incomplete, partially due to the lack of their precise phase analyses under various boundary conditions. Here we present nine speleothem oxygen-isotope records from mid-to-low-latitude monsoon regimes with sub-centennial age precision and multi-annual resolution, spanning the Heinrich Stadial 2 (HS2) - a millennial-scale event that occurred at the Last Glacial Maximum. Our data suggests that the Greenland and Antarctic ice-core chronologies require +320- and +400-year adjustments, respectively, supported by extant volcanic evidence and radiocarbon ages. Our chronological framework shows a synchronous HS2 onset globally. Our records precisely characterize a centennial-scale abrupt "tropical atmospheric seesaw" superimposed on the conventional "bipolar seesaw" at the beginning of HS2, implying a unique response/feedback from low-latitude hydroclimate. Together with our observation of an early South American monsoon shift at the HS2 termination, we suggest a more active role of low-latitude hydroclimate dynamics underlying millennial events than previously thought.

5.
Nat Commun ; 13(1): 5443, 2022 09 16.
Article En | MEDLINE | ID: mdl-36114188

Here we use high-precision carbon isotope data (δ13C-CO2) to show atmospheric CO2 during Marine Isotope Stage 4 (MIS 4, ~70.5-59 ka) was controlled by a succession of millennial-scale processes. Enriched δ13C-CO2 during peak glaciation suggests increased ocean carbon storage. Variations in δ13C-CO2 in early MIS 4 suggest multiple processes were active during CO2 drawdown, potentially including decreased land carbon and decreased Southern Ocean air-sea gas exchange superposed on increased ocean carbon storage. CO2 remained low during MIS 4 while δ13C-CO2 fluctuations suggest changes in Southern Ocean and North Atlantic air-sea gas exchange. A 7 ppm increase in CO2 at the onset of Dansgaard-Oeschger event 19 (72.1 ka) and 27 ppm increase in CO2 during late MIS 4 (Heinrich Stadial 6, ~63.5-60 ka) involved additions of isotopically light carbon to the atmosphere. The terrestrial biosphere and Southern Ocean air-sea gas exchange are possible sources, with the latter event also involving decreased ocean carbon storage.


Carbon Dioxide , Ice Cover , Carbon , Carbon Cycle , Carbon Isotopes , Seawater
6.
Sci Adv ; 7(51): eabj9341, 2021 Dec 17.
Article En | MEDLINE | ID: mdl-34910502

The history of atmospheric oxygen (PO2) and the processes that act to regulate it remain enigmatic because of difficulties in quantitative reconstructions using indirect proxies. Here, we extend the ice-core record of PO2 using 1.5-million-year-old (Ma) discontinuous ice samples drilled from Allan Hills Blue Ice Area, East Antarctica. No statistically significant difference exists in PO2 between samples at 1.5 Ma and 810 thousand years (ka), suggesting that the Late-Pleistocene imbalance in O2 sources and sinks began around the time of the transition from 40- to 100-ka glacial cycles in the Mid-Pleistocene between ~1.2 Ma and 700 ka. The absence of a coeval secular increase in atmospheric CO2 over the past ~1 Ma requires negative feedback mechanisms such as Pco2-dependent silicate weathering. Fast processes must also act to suppress the immediate Pco2 increase because of the imbalance in O2 sinks over sources beginning in the Mid-Pleistocene.

8.
Proc Natl Acad Sci U S A ; 118(36)2021 09 07.
Article En | MEDLINE | ID: mdl-34426524

The atmospheric history of molecular hydrogen (H2) from 1852 to 2003 was reconstructed from measurements of firn air collected at Megadunes, Antarctica. The reconstruction shows that H2 levels in the southern hemisphere were roughly constant near 330 parts per billion (ppb; nmol H2 mol-1 air) during the mid to late 1800s. Over the twentieth century, H2 levels rose by about 70% to 550 ppb. The reconstruction shows good agreement with the H2 atmospheric history based on firn air measurements from the South Pole. The broad trends in atmospheric H2 over the twentieth century can be explained by increased methane oxidation and anthropogenic emissions. The H2 rise shows no evidence of deceleration during the last quarter of the twentieth century despite an expected reduction in automotive emissions following more stringent regulations. During the late twentieth century, atmospheric CO levels decreased due to a reduction in automotive emissions. It is surprising that atmospheric H2 did not respond similarly as automotive exhaust is thought to be the dominant source of anthropogenic H2. The monotonic late twentieth century rise in H2 levels is consistent with late twentieth-century flask air measurements from high southern latitudes. An additional unknown source of H2 is needed to explain twentieth-century trends in atmospheric H2 and to resolve the discrepancy between bottom-up and top-down estimates of the anthropogenic source term. The firn air-based atmospheric history of H2 provides a baseline from which to assess human impact on the H2 cycle over the last 150 y and validate models that will be used to project future trends in atmospheric composition as H2 becomes a more common energy source.


Anthropogenic Effects , Atmosphere , Environmental Monitoring/methods , Hydrogen/analysis , Antarctic Regions , Humans , Models, Theoretical , Vehicle Emissions
9.
Science ; 372(6546): 1097-1101, 2021 06 04.
Article En | MEDLINE | ID: mdl-34083489

Water-stable isotopes in polar ice cores are a widely used temperature proxy in paleoclimate reconstruction, yet calibration remains challenging in East Antarctica. Here, we reconstruct the magnitude and spatial pattern of Last Glacial Maximum surface cooling in Antarctica using borehole thermometry and firn properties in seven ice cores. West Antarctic sites cooled ~10°C relative to the preindustrial period. East Antarctic sites show a range from ~4° to ~7°C cooling, which is consistent with the results of global climate models when the effects of topographic changes indicated with ice core air-content data are included, but less than those indicated with the use of water-stable isotopes calibrated against modern spatial gradients. An altered Antarctic temperature inversion during the glacial reconciles our estimates with water-isotope observations.

10.
Sci Adv ; 7(25)2021 Jun.
Article En | MEDLINE | ID: mdl-34134984

Abrupt climate changes during the last deglaciation have been well preserved in proxy records across the globe. However, one long-standing puzzle is the apparent absence of the onset of the Heinrich Stadial 1 (HS1) cold event around 18 ka in Greenland ice core oxygen isotope δ18 O records, inconsistent with other proxies. Here, combining proxy records with an isotope-enabled transient deglacial simulation, we propose that a substantial HS1 cooling onset did indeed occur over the Arctic in winter. However, this cooling signal in the depleted oxygen isotopic composition is completely compensated by the enrichment because of the loss of winter precipitation in response to sea ice expansion associated with AMOC slowdown during extreme glacial climate. In contrast, the Arctic summer warmed during HS1 and YD because of increased insolation and greenhouse gases, consistent with snowline reconstructions. Our work suggests that Greenland δ18 O may substantially underestimate temperature variability during cold glacial conditions.

11.
Nature ; 593(7858): 228-232, 2021 05.
Article En | MEDLINE | ID: mdl-33981051

The magnitude of global cooling during the Last Glacial Maximum (LGM, the coldest multimillennial interval of the last glacial period) is an important constraint for evaluating estimates of Earth's climate sensitivity1,2. Reliable LGM temperatures come from high-latitude ice cores3,4, but substantial disagreement exists between proxy records in the low latitudes1,5-8, where quantitative low-elevation records on land are scarce. Filling this data gap, noble gases in ancient groundwater record past land surface temperatures through a direct physical relationship that is rooted in their temperature-dependent solubility in water9,10. Dissolved noble gases are suitable tracers of LGM temperature because of their complete insensitivity to biological and chemical processes and the ubiquity of LGM-aged groundwater around the globe11,12. However, although several individual noble gas studies have found substantial tropical LGM cooling13-16, they have used different methodologies and provide limited spatial coverage. Here we use noble gases in groundwater to show that the low-altitude, low-to-mid-latitude land surface (45 degrees south to 35 degrees north) cooled by 5.8 ± 0.6 degrees Celsius (mean ± 95% confidence interval) during the LGM. Our analysis includes four decades of groundwater noble gas data from six continents, along with new records from the tropics, all of which were interpreted using the same physical framework. Our land-based result broadly supports a recent reconstruction based on marine proxy data assimilation1 that suggested greater climate sensitivity than previous estimates5-7.


Climate Change/history , Climate , Cold Temperature , Ice Cover , Altitude , Groundwater/chemistry , History, Ancient , Noble Gases/analysis , Reproducibility of Results , Solubility
12.
Proc Natl Acad Sci U S A ; 117(38): 23408-23417, 2020 09 22.
Article En | MEDLINE | ID: mdl-32900942

The Younger Dryas (YD), arguably the most widely studied millennial-scale extreme climate event, was characterized by diverse hydroclimate shifts globally and severe cooling at high northern latitudes that abruptly punctuated the warming trend from the last glacial to the present interglacial. To date, a precise understanding of its trigger, propagation, and termination remains elusive. Here, we present speleothem oxygen-isotope data that, in concert with other proxy records, allow us to quantify the timing of the YD onset and termination at an unprecedented subcentennial temporal precision across the North Atlantic, Asian Monsoon-Westerlies, and South American Monsoon regions. Our analysis suggests that the onsets of YD in the North Atlantic (12,870 ± 30 B.P.) and the Asian Monsoon-Westerlies region are essentially synchronous within a few decades and lead the onset in Antarctica, implying a north-to-south climate signal propagation via both atmospheric (decadal-time scale) and oceanic (centennial-time scale) processes, similar to the Dansgaard-Oeschger events during the last glacial period. In contrast, the YD termination may have started first in Antarctica at ∼11,900 B.P., or perhaps even earlier in the western tropical Pacific, followed by the North Atlantic between ∼11,700 ± 40 and 11,610 ± 40 B.P. These observations suggest that the initial YD termination might have originated in the Southern Hemisphere and/or the tropical Pacific, indicating a Southern Hemisphere/tropics to North Atlantic-Asian Monsoon-Westerlies directionality of climatic recovery.

13.
Nat Commun ; 10(1): 5739, 2019 12 16.
Article En | MEDLINE | ID: mdl-31844053

Constraining the magnitude of past hydrological change may improve understanding and predictions of future shifts in water availability. Here we demonstrate that water-table depth, a sensitive indicator of hydroclimate, can be quantitatively reconstructed using Kr and Xe isotopes in groundwater. We present the first-ever measurements of these dissolved noble gas isotopes in groundwater at high precision (≤0.005‰ amu-1; 1σ), which reveal depth-proportional signals set by gravitational settling in soil air at the time of recharge. Analyses of California groundwater successfully reproduce modern groundwater levels and indicate a 17.9 ± 1.3 m (±1 SE) decline in water-table depth in Southern California during the last deglaciation. This hydroclimatic transition from the wetter glacial period to more arid Holocene accompanies a surface warming of 6.2 ± 0.6 °C (±1 SE). This new hydroclimate proxy builds upon an existing paleo-temperature application of noble gases and may identify regions prone to future hydrological change.

14.
Nature ; 574(7780): 663-666, 2019 10.
Article En | MEDLINE | ID: mdl-31666720

Over the past eight hundred thousand years, glacial-interglacial cycles oscillated with a period of one hundred thousand years ('100k world'1). Ice core and ocean sediment data have shown that atmospheric carbon dioxide, Antarctic temperature, deep ocean temperature, and global ice volume correlated strongly with each other in the 100k world2-6. Between about 2.8 and 1.2 million years ago, glacial cycles were smaller in magnitude and shorter in duration ('40k world'7). Proxy data from deep-sea sediments suggest that the variability of atmospheric carbon dioxide in the 40k world was also lower than in the 100k world8-10, but we do not have direct observations of atmospheric greenhouse gases from this period. Here we report the recovery of stratigraphically discontinuous ice more than two million years old from the Allan Hills Blue Ice Area, East Antarctica. Concentrations of carbon dioxide and methane in ice core samples older than two million years have been altered by respiration, but some younger samples are pristine. The recovered ice cores extend direct observations of atmospheric carbon dioxide, methane, and Antarctic temperature (based on the deuterium/hydrogen isotope ratio δDice, a proxy for regional temperature) into the 40k world. All climate properties before eight hundred thousand years ago fall within the envelope of observations from continuous deep Antarctic ice cores that characterize the 100k world. However, the lowest measured carbon dioxide and methane concentrations and Antarctic temperature in the 40k world are well above glacial values from the past eight hundred thousand years. Our results confirm that the amplitudes of glacial-interglacial variations in atmospheric greenhouse gases and Antarctic climate were reduced in the 40k world, and that the transition from the 40k to the 100k world was accompanied by a decline in minimum carbon dioxide concentrations during glacial maxima.

15.
Proc Natl Acad Sci U S A ; 116(30): 14881-14886, 2019 07 23.
Article En | MEDLINE | ID: mdl-31285336

The energy imbalance at the top of the atmosphere determines the temporal evolution of the global climate, and vice versa changes in the climate system can alter the planetary energy fluxes. This interplay is fundamental to our understanding of Earth's heat budget and the climate system. However, even today, the direct measurement of global radiative fluxes is difficult, such that most assessments are based on changes in the total energy content of the climate system. We apply the same approach to estimate the long-term evolution of Earth's radiative imbalance in the past. New measurements of noble gas-derived mean ocean temperature from the European Project for Ice Coring in Antarctica Dome C ice core covering the last 40,000 y, combined with recent results from the West Antarctic Ice Sheet Divide ice core and the sea-level record, allow us to quantitatively reconstruct the history of the climate system energy budget. The temporal derivative of this quantity must be equal to the planetary radiative imbalance. During the deglaciation, a positive imbalance of typically +0.2 W⋅m-2 is maintained for ∼10,000 y, however, with two distinct peaks that reach up to 0.4 W⋅m-2 during times of substantially reduced Atlantic Meridional Overturning Circulation. We conclude that these peaks are related to net changes in ocean heat uptake, likely due to rapid changes in North Atlantic deep-water formation and their impact on the global radiative balance, while changes in cloud coverage, albeit uncertain, may also factor into the picture.

16.
Rapid Commun Mass Spectrom ; 32(10): 801-814, 2018 May 30.
Article En | MEDLINE | ID: mdl-29500867

RATIONALE: The global ocean constitutes the largest heat buffer in the global climate system, but little is known about its past changes. The isotopic and elemental ratios of heavy noble gases (krypton and xenon), together with argon and nitrogen in trapped air from ice cores, can be used to reconstruct past mean ocean temperatures (MOTs). Here we introduce two successively developed methods to measure these parameters with a sufficient precision to provide new constraints on past changes in MOT. METHODS: The air from an 800-g ice sample - containing roughly 80 mL STP air - is extracted and processed to be analyzed on two independent dual-inlet isotope ratio mass spectrometers. The primary isotope ratios (δ15 N, δ40 Ar and δ86 Kr values) are obtained with precisions in the range of 1 per meg (0.001‰) per mass unit. The three elemental ratio values δKr/N2 , δXe/N2 and δXe/Kr are obtained using sequential (non-simultaneous) peak-jumping, reaching precisions in the range of 0.1-0.3‰. RESULTS: The latest version of the method achieves a 30% to 50% better precision on the elemental ratios and a twofold better sample throughput than the previous one. The method development uncovered an unexpected source of artefactual gas fractionation in a closed system that is caused by adiabatic cooling and warming of gases (termed adiabatic fractionation) - a potential source of measurement artifacts in other methods. CONCLUSIONS: The precisions of the three elemental ratios δKr/N2 , δXe/N2 and δXe/Kr - which all contain the same MOT information - suggest smaller uncertainties for reconstructed MOTs (±0.3-0.1°C) than previous studies have attained. Due to different sensitivities of the noble gases to changes in MOT, δXe/N2 provides the best constraints on the MOT under the given precisions followed by δXe/Kr, and δKr/N2 ; however, using all of them helps to detect methodological artifacts and issues with ice quality.

17.
Proc Natl Acad Sci U S A ; 114(38): 10035-10040, 2017 09 19.
Article En | MEDLINE | ID: mdl-28874529

Glacial-state greenhouse gas concentrations and Southern Hemisphere climate conditions persisted until ∼17.7 ka, when a nearly synchronous acceleration in deglaciation was recorded in paleoclimate proxies in large parts of the Southern Hemisphere, with many changes ascribed to a sudden poleward shift in the Southern Hemisphere westerlies and subsequent climate impacts. We used high-resolution chemical measurements in the West Antarctic Ice Sheet Divide, Byrd, and other ice cores to document a unique, ∼192-y series of halogen-rich volcanic eruptions exactly at the start of accelerated deglaciation, with tephra identifying the nearby Mount Takahe volcano as the source. Extensive fallout from these massive eruptions has been found >2,800 km from Mount Takahe. Sulfur isotope anomalies and marked decreases in ice core bromine consistent with increased surface UV radiation indicate that the eruptions led to stratospheric ozone depletion. Rather than a highly improbable coincidence, circulation and climate changes extending from the Antarctic Peninsula to the subtropics-similar to those associated with modern stratospheric ozone depletion over Antarctica-plausibly link the Mount Takahe eruptions to the onset of accelerated Southern Hemisphere deglaciation ∼17.7 ka.

18.
Nature ; 548(7668): 443-446, 2017 08 23.
Article En | MEDLINE | ID: mdl-28836593

Methane (CH4) is a powerful greenhouse gas and plays a key part in global atmospheric chemistry. Natural geological emissions (fossil methane vented naturally from marine and terrestrial seeps and mud volcanoes) are thought to contribute around 52 teragrams of methane per year to the global methane source, about 10 per cent of the total, but both bottom-up methods (measuring emissions) and top-down approaches (measuring atmospheric mole fractions and isotopes) for constraining these geological emissions have been associated with large uncertainties. Here we use ice core measurements to quantify the absolute amount of radiocarbon-containing methane (14CH4) in the past atmosphere and show that geological methane emissions were no higher than 15.4 teragrams per year (95 per cent confidence), averaged over the abrupt warming event that occurred between the Younger Dryas and Preboreal intervals, approximately 11,600 years ago. Assuming that past geological methane emissions were no lower than today, our results indicate that current estimates of today's natural geological methane emissions (about 52 teragrams per year) are too high and, by extension, that current estimates of anthropogenic fossil methane emissions are too low. Our results also improve on and confirm earlier findings that the rapid increase of about 50 per cent in mole fraction of atmospheric methane at the Younger Dryas-Preboreal event was driven by contemporaneous methane from sources such as wetlands; our findings constrain the contribution from old carbon reservoirs (marine methane hydrates, permafrost and methane trapped under ice) to 19 per cent or less (95 per cent confidence). To the extent that the characteristics of the most recent deglaciation and the Younger Dryas-Preboreal warming are comparable to those of the current anthropogenic warming, our measurements suggest that large future atmospheric releases of methane from old carbon sources are unlikely to occur.


Atmosphere/chemistry , Global Warming/history , Methane/analysis , Methane/history , Carbon/analysis , Carbon/chemistry , Fossil Fuels/analysis , History, Ancient , Ice/analysis , Methane/chemistry , Radiometric Dating , Wetlands
19.
Proc Natl Acad Sci U S A ; 113(50): 14249-14254, 2016 12 13.
Article En | MEDLINE | ID: mdl-27911783

The most recent glacial to interglacial transition constitutes a remarkable natural experiment for learning how Earth's climate responds to various forcings, including a rise in atmospheric CO2 This transition has left a direct thermal remnant in the polar ice sheets, where the exceptional purity and continual accumulation of ice permit analyses not possible in other settings. For Antarctica, the deglacial warming has previously been constrained only by the water isotopic composition in ice cores, without an absolute thermometric assessment of the isotopes' sensitivity to temperature. To overcome this limitation, we measured temperatures in a deep borehole and analyzed them together with ice-core data to reconstruct the surface temperature history of West Antarctica. The deglacial warming was [Formula: see text]C, approximately two to three times the global average, in agreement with theoretical expectations for Antarctic amplification of planetary temperature changes. Consistent with evidence from glacier retreat in Southern Hemisphere mountain ranges, the Antarctic warming was mostly completed by 15 kyBP, several millennia earlier than in the Northern Hemisphere. These results constrain the role of variable oceanic heat transport between hemispheres during deglaciation and quantitatively bound the direct influence of global climate forcings on Antarctic temperature. Although climate models perform well on average in this context, some recent syntheses of deglacial climate history have underestimated Antarctic warming and the models with lowest sensitivity can be discounted.

20.
Proc Natl Acad Sci U S A ; 113(13): 3465-70, 2016 Mar 29.
Article En | MEDLINE | ID: mdl-26976561

An understanding of the mechanisms that control CO2 change during glacial-interglacial cycles remains elusive. Here we help to constrain changing sources with a high-precision, high-resolution deglacial record of the stable isotopic composition of carbon in CO2(δ(13)C-CO2) in air extracted from ice samples from Taylor Glacier, Antarctica. During the initial rise in atmospheric CO2 from 17.6 to 15.5 ka, these data demarcate a decrease in δ(13)C-CO2, likely due to a weakened oceanic biological pump. From 15.5 to 11.5 ka, the continued atmospheric CO2 rise of 40 ppm is associated with small changes in δ(13)C-CO2, consistent with a nearly equal contribution from a further weakening of the biological pump and rising ocean temperature. These two trends, related to marine sources, are punctuated at 16.3 and 12.9 ka with abrupt, century-scale perturbations in δ(13)C-CO2 that suggest rapid oxidation of organic land carbon or enhanced air-sea gas exchange in the Southern Ocean. Additional century-scale increases in atmospheric CO2 coincident with increases in atmospheric CH4 and Northern Hemisphere temperature at the onset of the Bølling (14.6-14.3 ka) and Holocene (11.6-11.4 ka) intervals are associated with small changes in δ(13)C-CO2, suggesting a combination of sources that included rising surface ocean temperature.

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