Pre-aged terrigenous organic carbon biases ocean ventilation-age reconstructions in the North Atlantic.

Changes in ocean ventilation have been pivotal in regulating carbon sequestration and release on centennial to millennial timescales. However, paleoceanographic reconstructions documenting changes in deep-ocean ventilation using 14C dating, may bear multidimensional explanations, obfuscating the roles of ocean ventilation played on climate evolution. Here, we show that previously inferred poorly ventilated conditions in the North Atlantic were linked to enhanced pre-aged organic carbon (OC) input during Heinrich Stadial 1 (HS1). The 14C age of sedimentary OC was approximately 13,345 ± 692 years older than the coeval foraminifera in the central North Atlantic during HS1, which is coupled to a ventilation age of 5,169 ± 660 years. Old OC was mainly of terrigenous origin and exported to the North Atlantic by ice-rafting. Remineralization of old terrigenous OC in the ocean may have contributed to, at least in part, the anomalously old ventilation ages reported for the high-latitude North Atlantic during HS1.

Complex spatio-temporal structure of the Holocene Thermal Maximum.

Inconsistencies between Holocene climate reconstructions and numerical model simulations question the robustness of climate models and proxy temperature records. Climate reconstructions suggest an early-middle Holocene Thermal Maximum (HTM) followed by gradual cooling, whereas climate models indicate continuous warming. This discrepancy either implies seasonal biases in proxy-based climate reconstructions, or that the climate model sensitivity to forcings and feedbacks needs to be reevaluated. Here, we analyze a global database of Holocene paleotemperature records to investigate the spatiotemporal structure of the HTM. Continental proxy records at mid and high latitudes of the Northern Hemisphere portray a "classic" HTM (8-4 ka). In contrast, marine proxy records from the same latitudes reveal an earlier HTM (11-7ka), while a clear temperature anomaly is missing in the tropics. The results indicate a heterogeneous response to climate forcing and highlight the lack of globally synchronous HTM.

Chromium Cycling in Redox-Stratified Basins Challenges δ53Cr Paleoredox Proxy Applications.

Chromium stable isotope composition (δ53Cr) is a promising tracer for redox conditions throughout Earth's history; however, the geochemical controls of δ53Cr have not been assessed in modern redox-stratified basins. We present new chromium (Cr) concentration and δ53Cr data in dissolved, sinking particulate, and sediment samples from the redox-stratified Lake Cadagno (Switzerland), a modern Proterozoic ocean analog. These data demonstrate isotope fractionation during incomplete (non-quantitative) reduction and removal of Cr above the chemocline, driving isotopically light Cr accumulation in euxinic deep waters. Sediment authigenic Cr is isotopically distinct from overlying waters but comparable to average continental crust. New and published data from other redox-stratified basins show analogous patterns. This challenges assumptions from δ53Cr paleoredox applications that quantitative Cr reduction and removal limits isotope fractionation. Instead, fractionation from non-quantitative Cr removal leads to sedimentary records offset from overlying waters and not reflecting high δ53Cr from oxidative continental weathering.

Deglacial patterns of South Pacific overturning inferred from 231Pa and 230Th.

The millennial-scale variability of the Atlantic Meridional Overturning Circulation (AMOC) is well documented for the last glacial termination and beyond. Despite its importance for the climate system, the evolution of the South Pacific overturning circulation (SPOC) is by far less well understood. A recently published study highlights the potential applicability of the 231Pa/230Th-proxy in the Pacific. Here, we present five sedimentary down-core profiles of 231Pa/230Th-ratios measured on a depth transect from the Pacific sector of the Southern Ocean to test this hypothesis using downcore records. Our data are consistent with an increase in SPOC as early as 20 ka that peaked during Heinrich Stadial 1. The timing indicates that the SPOC did not simply react to AMOC changes via the bipolar seesaw but were triggered via Southern Hemisphere processes.

Southern Ocean upwelling, Earth's obliquity, and glacial-interglacial atmospheric CO2 change.

Previous studies have suggested that during the late Pleistocene ice ages, surface-deep exchange was somehow weakened in the Southern Ocean's Antarctic Zone, which reduced the leakage of deeply sequestered carbon dioxide and thus contributed to the lower atmospheric carbon dioxide levels of the ice ages. Here, high-resolution diatom-bound nitrogen isotope measurements from the Indian sector of the Antarctic Zone reveal three modes of change in Southern Westerly Wind-driven upwelling, each affecting atmospheric carbon dioxide. Two modes, related to global climate and the bipolar seesaw, have been proposed previously. The third mode-which arises from the meridional temperature gradient as affected by Earth's obliquity (axial tilt)-can explain the lag of atmospheric carbon dioxide behind climate during glacial inception and deglaciation. This obliquity-induced lag, in turn, makes carbon dioxide a delayed climate amplifier in the late Pleistocene glacial cycles.

Glacial heterogeneity in Southern Ocean carbon storage abated by fast South Indian deglacial carbon release.

Past changes in ocean 14C disequilibria have been suggested to reflect the Southern Ocean control on global exogenic carbon cycling. Yet, the volumetric extent of the glacial carbon pool and the deglacial mechanisms contributing to release remineralized carbon, particularly from regions with enhanced mixing today, remain insufficiently constrained. Here, we reconstruct the deglacial ventilation history of the South Indian upwelling hotspot near Kerguelen Island, using high-resolution 14C-dating of smaller-than-conventional foraminiferal samples and multi-proxy deep-ocean oxygen estimates. We find marked regional differences in Southern Ocean overturning with distinct South Indian fingerprints on (early de-)glacial atmospheric CO2 change. The dissipation of this heterogeneity commenced 14.6 kyr ago, signaling the onset of modern-like, strong South Indian Ocean upwelling, likely promoted by rejuvenated Atlantic overturning. Our findings highlight the South Indian Ocean's capacity to influence atmospheric CO2 levels and amplify the impacts of inter-hemispheric climate variability on global carbon cycling within centuries and millennia.

Biological Control of Chromium Redox and Stable Isotope Composition in the Surface Ocean.

While chromium stable isotopes (δ53Cr) have received significant attention for their utility as a tracer of oxygen availability in the distant geological past, a mechanistic understanding of modern oceanic controls on Cr and δ53Cr is still lacking. Here we present total dissolved δ53Cr, concentrations of Cr (III) and total dissolved Cr, and net community productivity (NCP) from the North Pacific. Chromium concentrations show surface depletions in waters with elevated NCP, but not in lower productivity waters. Observed Cr deficits correspond well with calculated Cr export derived from NCP and Cr:C ratios of natural phytoplankton and marine particulates. Chromium (III) concentrations are stable over the diel cycle yet correlate with NCP, with maxima found in highly productive surface waters but not in lower productivity waters, indicating biological control on Cr (III). The relationship between Cr (III) and δ53Cr suggests that δ53Cr distributions may be controlled by the removal of isotopically light Cr (III) at an isotopic enrichment factor (∆53Cr) of -1.08‰ ± 0.25 relative to total dissolved δ53Cr, in agreement with the global δ53Cr-Cr fractionation factor (-0.82‰ ± 0.05). No perturbation to δ53Cr, Cr, or Cr (III) is observed in oxygen-depleted waters (~10 µmol/kg), suggesting no strong control by O2 availability, in agreement with other recent studies. Therefore, we propose that biological productivity is the primary control on Cr and δ53Cr in the modern ocean. Consequently, δ53Cr records in marine sediments may not faithfully record oxygen availability in the Late Quaternary. Instead, our data demonstrate that δ53Cr records may be a useful tracer for biological productivity.

The residence time of Southern Ocean surface waters and the 100,000-year ice age cycle.

From 1.25 million to 700,000 years ago, the ice age cycle deepened and lengthened from 41,000- to 100,000-year periodicity, a transition that remains unexplained. Using surface- and bottom-dwelling foraminifera from the Antarctic Zone of the Southern Ocean to reconstruct the deep-to-surface supply of water during the ice ages of the past 1.5 million years, we found that a reduction in deep water supply and a concomitant freshening of the surface ocean coincided with the emergence of the high-amplitude 100,000-year glacial cycle. We propose that this slowing of deep-to-surface circulation (i.e., a longer residence time for Antarctic surface waters) prolonged ice ages by allowing the Antarctic halocline to strengthen, which increased the resistance of the Antarctic upper water column to orbitally paced drivers of carbon dioxide release.

Enhanced ocean-atmosphere carbon partitioning via the carbonate counter pump during the last deglacial.

Several synergistic mechanisms were likely involved in the last deglacial atmospheric pCO2 rise. Leading hypotheses invoke a release of deep-ocean carbon through enhanced convection in the Southern Ocean (SO) and concomitant decreased efficiency of the global soft-tissue pump (STP). However, the temporal evolution of both the STP and the carbonate counter pump (CCP) remains unclear, thus preventing the evaluation of their contributions to the pCO2 rise. Here we present sedimentary coccolith records combined with export production reconstructions from the Subantarctic Pacific to document the leverage the SO biological carbon pump (BCP) has imposed on deglacial pCO2. Our data suggest a weakening of BCP during the phases of carbon outgassing, due in part to an increased CCP along with higher surface ocean fertility and elevated [CO2aq]. We propose that reduced BCP efficiency combined with enhanced SO ventilation played a major role in propelling the Earth out of the last ice age.

Causes of ice age intensification across the Mid-Pleistocene Transition.

During the Mid-Pleistocene Transition (MPT; 1,200-800 kya), Earth's orbitally paced ice age cycles intensified, lengthened from ∼40,000 (∼40 ky) to ∼100 ky, and became distinctly asymmetrical. Testing hypotheses that implicate changing atmospheric CO2 levels as a driver of the MPT has proven difficult with available observations. Here, we use orbitally resolved, boron isotope CO2 data to show that the glacial to interglacial CO2 difference increased from ∼43 to ∼75 µatm across the MPT, mainly because of lower glacial CO2 levels. Through carbon cycle modeling, we attribute this decline primarily to the initiation of substantive dust-borne iron fertilization of the Southern Ocean during peak glacial stages. We also observe a twofold steepening of the relationship between sea level and CO2-related climate forcing that is suggestive of a change in the dynamics that govern ice sheet stability, such as that expected from the removal of subglacial regolith or interhemispheric ice sheet phase-locking. We argue that neither ice sheet dynamics nor CO2 change in isolation can explain the MPT. Instead, we infer that the MPT was initiated by a change in ice sheet dynamics and that longer and deeper post-MPT ice ages were sustained by carbon cycle feedbacks related to dust fertilization of the Southern Ocean as a consequence of larger ice sheets.

Active Pacific meridional overturning circulation (PMOC) during the warm Pliocene.

An essential element of modern ocean circulation and climate is the Atlantic meridional overturning circulation (AMOC), which includes deep-water formation in the subarctic North Atlantic. However, a comparable overturning circulation is absent in the Pacific, the world's largest ocean, where relatively fresh surface waters inhibit North Pacific deep convection. We present complementary measurement and modeling evidence that the warm, ~400-ppmv (parts per million by volume) CO2 world of the Pliocene supported subarctic North Pacific deep-water formation and a Pacific meridional overturning circulation (PMOC) cell. In Pliocene subarctic North Pacific sediments, we report orbitally paced maxima in calcium carbonate accumulation rate, with accompanying pigment and total organic carbon measurements supporting deep-ocean ventilation-driven preservation as their cause. Together with high accumulation rates of biogenic opal, these findings require vigorous bidirectional communication between surface waters and interior waters down to ~3 km in the western subarctic North Pacific, implying deep convection. Redox-sensitive trace metal data provide further evidence of higher Pliocene deep-ocean ventilation before the 2.73-Ma (million years) transition. This observational analysis is supported by climate modeling results, demonstrating that atmospheric moisture transport changes, in response to the reduced meridional sea surface temperature gradients of the Pliocene, were capable of eroding the halocline, leading to deep-water formation in the western subarctic Pacific and a strong PMOC. This second Northern Hemisphere overturning cell has important implications for heat transport, the ocean/atmosphere cycle of carbon, and potentially the equilibrium response of the Pacific to global warming.

Ocean dynamics, not dust, have controlled equatorial Pacific productivity over the past 500,000 years.

Biological productivity in the equatorial Pacific is relatively high compared with other low-latitude regimes, especially east of the dateline, where divergence driven by the trade winds brings nutrient-rich waters of the Equatorial Undercurrent to the surface. The equatorial Pacific is one of the three principal high-nutrient low-chlorophyll ocean regimes where biological utilization of nitrate and phosphate is limited, in part, by the availability of iron. Throughout most of the equatorial Pacific, upwelling of water from the Equatorial Undercurrent supplies far more dissolved iron than is delivered by dust, by as much as two orders of magnitude. Nevertheless, recent studies have inferred that the greater supply of dust during ice ages stimulated greater utilization of nutrients within the region of upwelling on the equator, thereby contributing to the sequestration of carbon in the ocean interior. Here we present proxy records for dust and for biological productivity over the past 500 ky at three sites spanning the breadth of the equatorial Pacific Ocean to test the dust fertilization hypothesis. Dust supply peaked under glacial conditions, consistent with previous studies, whereas proxies of export production exhibit maxima during ice age terminations. Temporal decoupling between dust supply and biological productivity indicates that other factors, likely involving ocean dynamics, played a greater role than dust in regulating equatorial Pacific productivity.

Biological and physical controls in the Southern Ocean on past millennial-scale atmospheric CO2 changes.

Millennial-scale climate changes during the last glacial period and deglaciation were accompanied by rapid changes in atmospheric CO2 that remain unexplained. While the role of the Southern Ocean as a 'control valve' on ocean-atmosphere CO2 exchange has been emphasized, the exact nature of this role, in particular the relative contributions of physical (for example, ocean dynamics and air-sea gas exchange) versus biological processes (for example, export productivity), remains poorly constrained. Here we combine reconstructions of bottom-water [O2], export production and (14)C ventilation ages in the sub-Antarctic Atlantic, and show that atmospheric CO2 pulses during the last glacial- and deglacial periods were consistently accompanied by decreases in the biological export of carbon and increases in deep-ocean ventilation via southern-sourced water masses. These findings demonstrate how the Southern Ocean's 'organic carbon pump' has exerted a tight control on atmospheric CO2, and thus global climate, specifically via a synergy of both physical and biological processes.

Global pulses of organic carbon burial in deep-sea sediments during glacial maxima.

The burial of organic carbon in marine sediments removes carbon dioxide from the ocean-atmosphere pool, provides energy to the deep biosphere, and on geological timescales drives the oxygenation of the atmosphere. Here we quantify natural variations in the burial of organic carbon in deep-sea sediments over the last glacial cycle. Using a new data compilation of hundreds of sediment cores, we show that the accumulation rate of organic carbon in the deep sea was consistently higher (50%) during glacial maxima than during interglacials. The spatial pattern and temporal progression of the changes suggest that enhanced nutrient supply to parts of the surface ocean contributed to the glacial burial pulses, with likely additional contributions from more efficient transfer of organic matter to the deep sea and better preservation of organic matter due to reduced oxygen exposure. These results demonstrate a pronounced climate sensitivity for this global carbon cycle sink.

Covariation of deep Southern Ocean oxygenation and atmospheric CO2 through the last ice age.

No single mechanism can account for the full amplitude of past atmospheric carbon dioxide (CO2) concentration variability over glacial-interglacial cycles. A build-up of carbon in the deep ocean has been shown to have occurred during the Last Glacial Maximum. However, the mechanisms responsible for the release of the deeply sequestered carbon to the atmosphere at deglaciation, and the relative importance of deep ocean sequestration in regulating millennial-timescale variations in atmospheric CO2 concentration before the Last Glacial Maximum, have remained unclear. Here we present sedimentary redox-sensitive trace-metal records from the Antarctic Zone of the Southern Ocean that provide a reconstruction of transient changes in deep ocean oxygenation and, by inference, respired carbon storage throughout the last glacial cycle. Our data suggest that respired carbon was removed from the abyssal Southern Ocean during the Northern Hemisphere cold phases of the deglaciation, when atmospheric CO2 concentration increased rapidly, reflecting--at least in part--a combination of dwindling iron fertilization by dust and enhanced deep ocean ventilation. Furthermore, our records show that the observed covariation between atmospheric CO2 concentration and abyssal Southern Ocean oxygenation was maintained throughout most of the past 80,000 years. This suggests that on millennial timescales deep ocean circulation and iron fertilization in the Southern Ocean played a consistent role in modifying atmospheric CO2 concentration.

A stagnation event in the deep South Atlantic during the last interglacial period.

During the last interglacial period, global temperatures were ~2°C warmer than at present and sea level was 6 to 8 meters higher. Southern Ocean sediments reveal a spike in authigenic uranium 127,000 years ago, within the last interglacial, reflecting decreased oxygenation of deep water by Antarctic Bottom Water (AABW). Unlike ice age reductions in AABW, the interglacial stagnation event appears decoupled from open ocean conditions and may have resulted from coastal freshening due to mass loss from the Antarctic ice sheet. AABW reduction coincided with increased North Atlantic Deep Water (NADW) formation, and the subsequent reinvigoration in AABW coincided with reduced NADW formation. Thus, alternation of deep water formation between the Antarctic and the North Atlantic, believed to characterize ice ages, apparently also occurs in warm climates.

Iron fertilization of the Subantarctic ocean during the last ice age.

John H. Martin, who discovered widespread iron limitation of ocean productivity, proposed that dust-borne iron fertilization of Southern Ocean phytoplankton caused the ice age reduction in atmospheric carbon dioxide (CO2). In a sediment core from the Subantarctic Atlantic, we measured foraminifera-bound nitrogen isotopes to reconstruct ice age nitrate consumption, burial fluxes of iron, and proxies for productivity. Peak glacial times and millennial cold events are characterized by increases in dust flux, productivity, and the degree of nitrate consumption; this combination is uniquely consistent with Subantarctic iron fertilization. The associated strengthening of the Southern Ocean's biological pump can explain the lowering of CO2 at the transition from mid-climate states to full ice age conditions as well as the millennial-scale CO2 oscillations.

Southern Ocean dust-climate coupling over the past four million years.

Dust has the potential to modify global climate by influencing the radiative balance of the atmosphere and by supplying iron and other essential limiting micronutrients to the ocean. Indeed, dust supply to the Southern Ocean increases during ice ages, and 'iron fertilization' of the subantarctic zone may have contributed up to 40 parts per million by volume (p.p.m.v.) of the decrease (80-100 p.p.m.v.) in atmospheric carbon dioxide observed during late Pleistocene glacial cycles. So far, however, the magnitude of Southern Ocean dust deposition in earlier times and its role in the development and evolution of Pleistocene glacial cycles have remained unclear. Here we report a high-resolution record of dust and iron supply to the Southern Ocean over the past four million years, derived from the analysis of marine sediments from ODP Site 1090, located in the Atlantic sector of the subantarctic zone. The close correspondence of our dust and iron deposition records with Antarctic ice core reconstructions of dust flux covering the past 800,000 years (refs 8, 9) indicates that both of these archives record large-scale deposition changes that should apply to most of the Southern Ocean, validating previous interpretations of the ice core data. The extension of the record beyond the interval covered by the Antarctic ice cores reveals that, in contrast to the relatively gradual intensification of glacial cycles over the past three million years, Southern Ocean dust and iron flux rose sharply at the Mid-Pleistocene climatic transition around 1.25 million years ago. This finding complements previous observations over late Pleistocene glacial cycles, providing new evidence of a tight connection between high dust input to the Southern Ocean and the emergence of the deep glaciations that characterize the past one million years of Earth history.

Carbon dioxide release from the North Pacific abyss during the last deglaciation.

Atmospheric carbon dioxide concentrations were significantly lower during glacial periods than during intervening interglacial periods, but the mechanisms responsible for this difference remain uncertain. Many recent explanations call on greater carbon storage in a poorly ventilated deep ocean during glacial periods, but direct evidence regarding the ventilation and respired carbon content of the glacial deep ocean is sparse and often equivocal. Here we present sedimentary geochemical records from sites spanning the deep subarctic Pacific that--together with previously published results--show that a poorly ventilated water mass containing a high concentration of respired carbon dioxide occupied the North Pacific abyss during the Last Glacial Maximum. Despite an inferred increase in deep Southern Ocean ventilation during the first step of the deglaciation (18,000-15,000 years ago), we find no evidence for improved ventilation in the abyssal subarctic Pacific until a rapid transition approximately 14,600 years ago: this change was accompanied by an acceleration of export production from the surface waters above but only a small increase in atmospheric carbon dioxide concentration. We speculate that these changes were mechanistically linked to a roughly coeval increase in deep water formation in the North Atlantic, which flushed respired carbon dioxide from northern abyssal waters, but also increased the supply of nutrients to the upper ocean, leading to greater carbon dioxide sequestration at mid-depths and stalling the rise of atmospheric carbon dioxide concentrations. Our findings are qualitatively consistent with hypotheses invoking a deglacial flushing of respired carbon dioxide from an isolated, deep ocean reservoir, but suggest that the reservoir may have been released in stages, as vigorous deep water ventilation switched between North Atlantic and Southern Ocean source regions.