Abstract
For its greenhouse effects, atmospheric CO2 can critically influence the global climate on millennial and centennial timescales. Pleistocene atmospheric CO2 variations must involve changes in ocean storage of carbon, but the mechanisms and pathways of carbon transfer between the oceanic and atmospheric reservoirs are poorly understood due, in part, to complications associated with interpretation of carbonate system proxy data. Here we employ a recently developed approach to reconstruct upper Atlantic air–sea CO2 exchange signatures through the last deglaciation. Using this approach, proxy and model data each suggest that there was a net release of CO2 via the Atlantic sector of the Southern Ocean during the early deglaciation, which probably contributed to the millennial-scale atmospheric CO2 rise during Heinrich Stadial 1 at ~18.0–14.7 kyr ago. Moreover, our data reveal a previously unrecognized mechanism for the centennial-scale atmospheric CO2 rise at the onset of the Bølling warming event around 14.7 kyr ago, namely, the expansion of Antarctic Intermediate Water, a water mass that is especially inefficient at sequestering atmospheric CO2. Our findings highlight the role of the Southern Ocean outgassing and intermediate water-mass production and volume variations in governing millennial- and centennial-timescale atmospheric CO2 rises during the last deglaciation.
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Data availability
All new data are provided in Supplementary Data.
Change history
19 April 2022
A Correction to this paper has been published: https://doi.org/10.1038/s41561-022-00946-x
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Acknowledgements
We thank L. X. Wu for valuable discussions about AAIW, S. F. Gu for providing model outputs shown in Fig. 5 and E. J. Rohling for assisting with statistics. This study is supported by NSFC 42076056 (J.Y.) NSFC41991322 (Z.J.), ARC Discovery Projects DP190100894 (J.Y.) and ARC Future Fellowship FT140100993 (J.Y.) and FT180100606 (L.M.).
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J.Y. designed the project and wrote the manuscript. D.W.O. provided critical core materials for new 14C dating and discussed Cd/Ca timing. Z.J. accomplished 14C dating, counted Nps abundance for NEAP 4K and picked shells for trace element analyses. M.L. contributed to age-model discussion. X.J. assisted with trace element analyses, uncertainty calculations and figure preparation. N.E.U. and D.C.L. shared published data for GGC90 and discussed age model. N.M. provided NEAP 4K sediments. L.M. and J.S. assisted with model data. J.S. performed Rampfit analyses. C.X. assisted with literature data compilation and figure preparation. All commented on the manuscript.
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Extended data
Extended Data Fig. 1 Preindustrial Atlantic \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\) vs DICas as shown in Fig. 1.
Data are from ref. 15, based on the calculation method from ref. 16. Black curve represents the best fit of the data. Simply put, when a water mass sequesters more atmospheric CO2, it has lower \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\) and higher DICas, and vice versa. For example, adding CO2 into a package of water would increase its DICas. At the same time, because the added CO2 would convert some \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\) into bicarbonate, its \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\) should decrease. Thus, the negative \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\)–DICas correlation is exactly expected from the CO2 system theory30. See ref. 16 and Methods for detailed discussions.
Extended Data Fig. 2 \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\)/DICas sensitivity vs. \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{Norm}}}}}\).
\(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{Norm}}}}}\) = \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\) + 78. The sensitivity is calculated based on the method from ref. 16. The large circle indicates the average sensitivity (-0.48) for \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{Norm}}}}}\) ranges (shaded region) observed at sites GGC90 and NEAP 4K during the last deglaciation.
Extended Data Fig. 3 Effect of biogenic composition and global alkalinity changes on GGC90 \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\).
a, Biogenic composition effect. C/\(\left[ {{{{\mathrm{PO}}}}_4^{3 - }} \right]\) and R values represent Redfield ratio and rain ratio (that is, molar carbon ratio between soft and skeleton parts), respectively. b-d, Effect of global alkalinity (ALK) changes associated with carbonate compensation. Assuming little change in continental weathering, increased carbonate burial in the deep ocean92,93,94,95 and on shelves driven by sea level rise96,97,98 would decrease the global ALK (b) and DIC at a 2:1 ratio during the last deglaciation. These changes would lower seawater \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\) (c), even without any air-sea CO2 exchange. Taken this global ALK effect into account, \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\) at GGC90 would show a larger increase during the last deglacial (d), suggesting greater CO2 outgassing from the upper South Atlantic. Here we use a recent model-based global ALK change99 to demonstrate the global ALK effect. Using other ALK estimates may yield different amplitudes of \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\) changes, but the overall pattern should maintain. Due to the large and slow response of the global oceanic ALK reservoir, any global ALK change would affect \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\) would be gradual (c). As can be seen, even considering potential influences from biogenic composition and global ALK changes, deglacial \(\left[ {{{{\mathrm{CO}}}}_3^{2 - }} \right]_{{{{\mathrm{as}}}}}\) evolution pattern persists, supporting our interpretation in the main text.
Extended Data Fig. 4 Antarctic Zone opal flux data from different sectors of the Southern Ocean.
As can be seen, opal fluxes differ in absolute values (for example, much higher deglacial fluxes in the Atlantic sector core 13PC than in other cores) and patterns (for example, a substantial decline in the Atlantic core 13PC during Bølling/Allerød, which is not seen in other cores; sustained opal flux increase in PS75/072-4 during the Holocene, but not seen in other cores). These different patterns may reflect varying hydrological conditions between different sectors of the Southern Ocean. This warrants the use of additional proxies to check palaeoceanographic inferences based on opal fluxes. Opal flux data are from refs. 2,4,100. Literature data are plotted against their originally published age models.
Extended Data Fig. 5 Heterogeneous surface-water CO2 partial pressure (pCO2) in the Southern Ocean.
a, Spatial surface-water pCO2 during the preindustrial, based on the GLODAP data set15. Note that the data coverage is incomplete and should not be treated to reflect the annual mean conditions. b, Temporal surface water and atmospheric pCO2 gradient (ΔpCO2) at PS2498-1 from the South Atlantic. c, Temporal ΔpCO2 at MD97-2106 from the South Pacific (see also ref. 101). Surface-water pCO2 was heterogeneous in the Southern Ocean, both spatially and temporally. Despite the Southern Ocean being an overall source of CO2 to the atmosphere, some surface ocean regions had lower pCO2 than the atmosphere, possibly reflecting seasonal and hydrographical variations in surface conditions. When using surface data, this highlights the need to obtain data for different seasons at broad locations to gain complete information about the Southern Ocean’s role in atmospheric CO217. Literature data are plotted against their originally published age models.
Extended Data Fig. 6 Concurrent changes in atmospheric CO2 and ΔDICas in core GGC90 at the Bølling onset.
a, WDC ice-core atmospheric CO21. b, ΔDICas in core GGC90 (this study). The ramp fittings of atmospheric CO2 and ΔDICas records are indicated in gray and red lines, respectively. The estimated change-points (±standard errors) of the CO2 transition are: t1 (start) = 14.77±0.04 ka, t2 (end) = 14.63±0.03 ka. The estimated change-points (±standard errors) of the ΔDICas transition are: t1 (start) = 14.89±0.35 ka, t2 (end) = 14.53±0.34 ka. Note that the large errors with ΔDICas change-point dates are mainly sourced from the assumed uncertainties (±200 years) associated with surface reservoir ages used for age model constructions (Methods). The slightly broader ramp in ΔDICas at GGC90 is expected due to bioturbation. The results are based on 1,000 bootstrap replications. The black dash lines highlight the concurrence of the atmospheric and oceanic transitions. The analyses are based on Rampfit software89.
Extended Data Fig. 7 Increased AAIW mixing at GGC90 at the Bølling onset.
a, Core locations against modern seawater salinity15. b, Pa/Th33. Everything else being equal, NADW invigoration at the Bølling onset (vertical yellow bar) would decrease εNd at GGC90. To prevent any εNd decline at GGC90, a concomitant increase in AAIW production would be required. c, GGC90 εNd102 compared with records from high latitudes North [eastern basin: BOFS 17K103; western basin: KNR198 cores104] and South [curves: TNO57-21105 and MD07-3076Q106; circles: deep-sea corals107] Atlantic. At the Bølling onset, GGC90 εNd shifted towards southern-sourced water (SSW) compositions (light blue shading), suggesting more AAIW mixing. d, Deep Atlantic εNd104 became even less radiogenic than shallower water εNd (grey shading), possibly linked to enhanced weathering of the North America104. e, Authigenic εNd at the Blake Bahama Outer Ridge102. In d and e, εNd declines at the Bølling onset possibly suggest addition of less radiogenic εNd during the southward transport of NADW102,104,108. This effect [for example, non-conservativeness during mixing109] would require even more AAIW mixing to maintain radiogenic εNd at GGC90 at the Bølling onset. Grey and light blue bars along y-axes indicate modern northern-sourced water (NSW) and SSW endmembers, respectively. These endmembers are thought to have changed in the past103,104,108. Literature data are plotted against their originally published age models.
Extended Data Fig. 8 Northward AAIW expansion at the Bølling onset.
a, Core locations against the modern seawater \(\left[ {{{{\mathrm{PO}}}}_4^{3 - }} \right]\) (shading)15. Solid and dashed white curves show, respectively, inferred AAIW geometries for HS1 and the Bølling onset, based on proxy and model results [δ13C42,44, εNd34,35,50, Cd/Ca41,62, and model43]. More data are needed to better constrain these geometries. b, Pa/Th at GGC533. c, Benthic Cd/Ca for the mid-depth Atlantic23,41,110,thisstudy. At NEAP 4K, C. wuellerstorfi Cd/Ca are adjusted by a factor of 2.2 to account for DCd difference between H. elegans and C. wuellerstorfi27,76. Vertical band shows the Bølling onset at ~14.7 ±0.25 ka. Compared to 26JPC (grey circles), NEAP 4K (blue circles) and GGC100 (blue squares) are more affected by NADW due to their deeper water depths and higher latitudinal locations (a). Without increased AAIW mixing, enhanced production of low-Cd NADW would have lowered Cd at 26JPC. Additionally, enhanced ventilation by NADW would decrease respired nutrient and thereby lower Cd at 26JPC. Thus, the sustained high Cd at 26JPC (and NEAP 4K) suggests increased mixing of AAIW at intermediate depths of the tropical North Atlantic at the Bølling onset, which is also supported by εNd data shown in Extended Data Fig. 9. Literature data are plotted against their originally published age models.
Extended Data Fig. 9 Increased AAIW mixing at the intermediate North Atlantic at the Bølling onset.
a, Core locations against modern seawater salinity15. b, Pa/Th, a proxy for NADW strength33. c, εNd at 26 JPC [discrete and connected circles are based on fish teeth and Fe-Mn leachates, respectively111,112]. Grey and light blue shadings and blue circles are defined in Extended Data Fig. 7. εNd at 26JPC was well within the range of NSW values (grey shading) during HS1, but shifted towards SSW values (light blue shading) at the Bølling onset. This is consistent with a northward expansion of AAIW at the Bølling onset41,42,43,110. Vertical grey and light blue bars along y-axis indicate modern NSW and SSW endmembers, respectively.
Extended Data Fig. 10 Northward transport of AAIW in the preindustrial Atlantic Ocean.
a, DICas–neutral density (γN) transect. b, DICas–salinity transect. Along isopycnal surfaces (γN = ~27.5 kg/m3 for AAIW), the low-DICas signals of AAIW can be traced at the intermediate depths in the high-latitude North Atlantic21,40,41,42,45,110 (a). Cross-equator transport of AAIW is also suggested by the northward extension of low-salinity waters at ~1 km (b). AAIW is found at ~500-1200 m94. Latest analyses suggest AAIW is distributed across most of the Atlantic up to ~30°N95. Because at least part of intermediate waters in the North Atlantic would be entrained to form NADW21,42,45, northward AAIW expansion would affect NADW’s DICas values. At the Bølling onset, our and previous results41,43,54,110,111,112 suggest a sudden northward expansion of AAIW (Extended Data Figs. 7–9) with an effect to lower DICas and thus atmospheric CO2 sequestration efficiency of NADW. Map generated using Ocean Data View based on the GLODAP data set15,46.
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Yu, J., Oppo, D.W., Jin, Z. et al. Millennial and centennial CO2 release from the Southern Ocean during the last deglaciation. Nat. Geosci. 15, 293–299 (2022). https://doi.org/10.1038/s41561-022-00910-9
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DOI: https://doi.org/10.1038/s41561-022-00910-9
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