Effect of iron supply on Southern Ocean CO2 uptake and implications for glacial atmospheric CO2

Photosynthesis by marine phytoplankton in the Southern Ocean, and the associated uptake of carbon, is thought to be currently limited by the availability of iron. One implication of this limitation is that a larger iron supply to the region in glacial times could have stimulated algal photosynthesis, leading to lower concentrations of atmospheric CO2. Similarly, it has been proposed that artificial iron fertilization of the oceans might increase future carbon sequestration. Here we report data from a whole-ecosystem test of the iron-limitation hypothesis in the Southern Ocean, which show that surface uptake of atmospheric CO2 and uptake ratios of silica to carbon by phytoplankton were strongly influenced by nanomolar increases of iron concentration. We use these results to inform a model of global carbon and ocean nutrients, forced with atmospheric iron fluxes to the region derived from the Vostok ice-core dust record. During glacial periods, predicted magnitudes and timings of atmospheric CO2 changes match ice-core records well. At glacial terminations, the model suggests that forcing of Southern Ocean biota by iron caused the initial approximately 40 p.p.m. of glacial-interglacial CO2 change, but other mechanisms must have accounted for the remaining 40 p.p.m. increase. The experiment also confirms that modest sequestration of atmospheric CO2 by artificial additions of iron to the Southern Ocean is in principle possible, although the period and geographical extent over which sequestration would be effective remain poorly known.     

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.     

Oceanic Cd/P ratio and nutrient utilization in the glacial Southern Ocean

During glacial periods, low atmospheric carbon dioxide concentration has been associated with increased oceanic carbon uptake, particularly in the southern oceans. The mechanism involved remains unclear. Because ocean productivity is strongly influenced by nutrient levels, palaeo-oceanographic proxies have been applied to investigate nutrient utilization in surface water across glacial transitions. Here we show that present-day cadmium and phosphorus concentrations in the global oceans can be explained by a chemical fractionation during particle formation, whereby uptake of cadmium occurs in preference to uptake of phosphorus. This allows the reconstruction of past surface water phosphate concentrations from the cadmium/calcium ratio of planktonic foraminifera. Results from the Last Glacial Maximum show similar phosphate utilization in the subantarctic to that of today, but much smaller utilization in the polar Southern Ocean, in a model that is consistent with the expansion of glacial sea ice and which can reconcile all proxy records of polar nutrient utilization. By restricting communication between the ocean and atmosphere, sea ice expansion also provides a mechanism for reduced CO2 release by the Southern Ocean and lower glacial atmospheric CO2.     

Southern Ocean sea-ice extent, productivity and iron flux over the past eight glacial cycles

Sea ice and dust flux increased greatly in the Southern Ocean during the last glacial period. Palaeorecords provide contradictory evidence about marine productivity in this region, but beyond one glacial cycle, data were sparse. Here we present continuous chemical proxy data spanning the last eight glacial cycles (740,000 years) from the Dome C Antarctic ice core. These data constrain winter sea-ice extent in the Indian Ocean, Southern Ocean biogenic productivity and Patagonian climatic conditions. We found that maximum sea-ice extent is closely tied to Antarctic temperature on multi-millennial timescales, but less so on shorter timescales. Biological dimethylsulphide emissions south of the polar front seem to have changed little with climate, suggesting that sulphur compounds were not active in climate regulation. We observe large glacial-interglacial contrasts in iron deposition, which we infer reflects strongly changing Patagonian conditions. During glacial terminations, changes in Patagonia apparently preceded sea-ice reduction, indicating that multiple mechanisms may be responsible for different phases of CO2 increase during glacial terminations. We observe no changes in internal climatic feedbacks that could have caused the change in amplitude of Antarctic temperature variations observed 440,000 years ago.     

Covariation of carbon dioxide and temperature from the Vostok ice core after deuterium-excess correction

Ice-core measurements of carbon dioxide and the deuterium palaeothermometer reveal significant covariation of temperature and atmospheric CO2 concentrations throughout the climate cycles of the past ice ages. This covariation provides compelling evidence that CO2 is an important forcing factor for climate. But this interpretation is challenged by some substantial mismatches of the CO2 and deuterium records, especially during the onset of the last glaciation, about 120 kyr ago. Here we incorporate measurements of deuterium excess from Vostok in the temperature reconstruction and show that much of the mismatch is an artefact caused by variations of climate in the water vapour source regions. Using a model that corrects for this effect, we derive a new estimate for the covariation of CO2 and temperature, of r2 = 0.89 for the past 150 kyr and r2 = 0.84 for the period 350-150 kyr ago. Given the complexity of the biogeochemical systems involved, this close relationship strongly supports the importance of carbon dioxide as a forcing factor of climate. Our results also suggest that the mechanisms responsible for the drawdown of CO2 may be more responsive to temperature than previously thought.     

Rapid Cenozoic glaciation of Antarctica induced by declining atmospheric CO2

The sudden, widespread glaciation of Antarctica and the associated shift towards colder temperatures at the Eocene/Oligocene boundary (approximately 34 million years ago) (refs 1-4) is one of the most fundamental reorganizations of global climate known in the geologic record. The glaciation of Antarctica has hitherto been thought to result from the tectonic opening of Southern Ocean gateways, which enabled the formation of the Antarctic Circumpolar Current and the subsequent thermal isolation of the Antarctic continent. Here we simulate the glacial inception and early growth of the East Antarctic Ice Sheet using a general circulation model with coupled components for atmosphere, ocean, ice sheet and sediment, and which incorporates palaeogeography, greenhouse gas, changing orbital parameters, and varying ocean heat transport. In our model, declining Cenozoic CO2 first leads to the formation of small, highly dynamic ice caps on high Antarctic plateaux. At a later time, a CO2 threshold is crossed, initiating ice-sheet height/mass-balance feedbacks that cause the ice caps to expand rapidly with large orbital variations, eventually coalescing into a continental-scale East Antarctic Ice Sheet. According to our simulation the opening of Southern Ocean gateways plays a secondary role in this transition, relative to CO2 concentration.     

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.     

Dust-climate couplings over the past 800,000 years from the EPICA Dome C ice core

Dust can affect the radiative balance of the atmosphere by absorbing or reflecting incoming solar radiation; it can also be a source of micronutrients, such as iron, to the ocean. It has been suggested that production, transport and deposition of dust is influenced by climatic changes on glacial-interglacial timescales. Here we present a high-resolution record of aeolian dust from the EPICA Dome C ice core in East Antarctica, which provides an undisturbed climate sequence over the past eight climatic cycles. We find that there is a significant correlation between dust flux and temperature records during glacial periods that is absent during interglacial periods. Our data suggest that dust flux is increasingly correlated with Antarctic temperature as the climate becomes colder. We interpret this as progressive coupling of the climates of Antarctic and lower latitudes. Limited changes in glacial-interglacial atmospheric transport time suggest that the sources and lifetime of dust are the main factors controlling the high glacial dust input. We propose that the observed approximately 25-fold increase in glacial dust flux over all eight glacial periods can be attributed to a strengthening of South American dust sources, together with a longer lifetime for atmospheric dust particles in the upper troposphere resulting from a reduced hydrological cycle during the ice ages.     

Evidence from U-Th dating against Northern Hemisphere forcing of the penultimate deglaciation

Milankovitch proposed that summer insolation at mid-latitudes in the Northern Hemisphere directly causes the ice-age climate cycles. This would imply that times of ice-sheet collapse should correspond to peaks in Northern Hemisphere June insolation. But the penultimate deglaciation has proved controversial because June insolation peaks 127 kyr ago whereas several records of past climate suggest that change may have occurred up to 15 kyr earlier. There is a clear signature of the penultimate deglaciation in marine oxygen-isotope records. But dating this event, which is significantly before the 14C age range, has not been possible. Here we date the penultimate deglaciation in a record from the Bahamas using a new U-Th isochron technique. After the necessary corrections for alpha-recoil mobility of 234U and 230Th and a small age correction for sediment mixing, the midpoint age for the penultimate deglaciation is determined to be 135 +/- 2.5 kyr ago. This age is consistent with some coral-based sea-level estimates, but it is difficult to reconcile with June Northern Hemisphere insolation as the trigger for the ice-age cycles. Potential alternative driving mechanisms for the ice-age cycles that are consistent with such an early date for the penultimate deglaciation are either the variability of the tropical ocean-atmosphere system or changes in atmospheric CO2 concentration controlled by a process in the Southern Hemisphere.     

Increased productivity in the subantarctic ocean during Heinrich events

Massive iceberg discharges from the Northern Hemisphere ice sheets, 'Heinrich events', coincided with the coldest periods of the last ice age. There is widespread evidence for Heinrich events and their profound impact on the climate and circulation of the North Atlantic Ocean, but their influence beyond that region remains uncertain. Here we use a combination of molecular fingerprints of algal productivity and radioisotope tracers of sedimentation to document eight periods of increased productivity in the subpolar Southern Ocean during the past 70,000 years that occurred within 1,000-2,000 years of a Northern Hemisphere Heinrich event. We discuss possible causes for such a link, including increased supply of iron from upwelling and increased stratification during the growing season, which imply an alteration of the global ocean circulation during Heinrich events. The mechanisms linking North Atlantic iceberg discharges with subantarctic productivity remain unclear at this point. We suggest that understanding how the Southern Ocean was altered during these extreme climate perturbations is critical to understanding the role of the ocean in climate change.     

Effect of natural iron fertilization on carbon sequestration in the Southern Ocean

The availability of iron limits primary productivity and the associated uptake of carbon over large areas of the ocean. Iron thus plays an important role in the carbon cycle, and changes in its supply to the surface ocean may have had a significant effect on atmospheric carbon dioxide concentrations over glacial-interglacial cycles. To date, the role of iron in carbon cycling has largely been assessed using short-term iron-addition experiments. It is difficult, however, to reliably assess the magnitude of carbon export to the ocean interior using such methods, and the short observational periods preclude extrapolation of the results to longer timescales. Here we report observations of a phytoplankton bloom induced by natural iron fertilization--an approach that offers the opportunity to overcome some of the limitations of short-term experiments. We found that a large phytoplankton bloom over the Kerguelen plateau in the Southern Ocean was sustained by the supply of iron and major nutrients to surface waters from iron-rich deep water below. The efficiency of fertilization, defined as the ratio of the carbon export to the amount of iron supplied, was at least ten times higher than previous estimates from short-term blooms induced by iron-addition experiments. This result sheds new light on the effect of long-term fertilization by iron and macronutrients on carbon sequestration, suggesting that changes in iron supply from below--as invoked in some palaeoclimatic and future climate change scenarios--may have a more significant effect on atmospheric carbon dioxide concentrations than previously thought.     

The effect of millennial-scale changes in Arabian Sea denitrification on atmospheric CO2.

Most global biogeochemical processes are known to respond to climate change, some of which have the capacity to produce feedbacks through the regulation of atmospheric greenhouse gases. Marine denitrification-the reduction of nitrate to gaseous nitrogen-is an important process in this regard, affecting greenhouse gas concentrations directly through the incidental production of nitrous oxide, and indirectly through modification of the marine nitrogen inventory and hence the biological pump for CO2. Although denitrification has been shown to vary with glacial-interglacial cycles, its response to more rapid climate change has not yet been well characterized. Here we present nitrogen isotope ratio, nitrogen content and chlorin abundance data from sediment cores with high accumulation rates on the Oman continental margin that reveal substantial millennial-scale variability in Arabian Sea denitrification and productivity during the last glacial period. The detailed correspondence of these changes with Dansgaard-Oeschger events recorded in Greenland ice cores indicates rapid, century-scale reorganization of the Arabian Sea ecosystem in response to climate excursions, mediated through the intensity of summer monsoonal upwelling. Considering the several-thousand-year residence time of fixed nitrogen in the ocean, the response of global marine productivity to changes in denitrification would have occurred at lower frequency and appears to be related to climatic and atmospheric CO2 oscillations observed in Antarctic ice cores between 20 and 60 kyr ago.     

The Southern Ocean biogeochemical divide

Modelling studies have demonstrated that the nutrient and carbon cycles in the Southern Ocean play a central role in setting the air-sea balance of CO(2) and global biological production. Box model studies first pointed out that an increase in nutrient utilization in the high latitudes results in a strong decrease in the atmospheric carbon dioxide partial pressure (pCO2). This early research led to two important ideas: high latitude regions are more important in determining atmospheric pCO2 than low latitudes, despite their much smaller area, and nutrient utilization and atmospheric pCO2 are tightly linked. Subsequent general circulation model simulations show that the Southern Ocean is the most important high latitude region in controlling pre-industrial atmospheric CO(2) because it serves as a lid to a larger volume of the deep ocean. Other studies point out the crucial role of the Southern Ocean in the uptake and storage of anthropogenic carbon dioxide and in controlling global biological production. Here we probe the system to determine whether certain regions of the Southern Ocean are more critical than others for air-sea CO(2) balance and the biological export production, by increasing surface nutrient drawdown in an ocean general circulation model. We demonstrate that atmospheric CO(2) and global biological export production are controlled by different regions of the Southern Ocean. The air-sea balance of carbon dioxide is controlled mainly by the biological pump and circulation in the Antarctic deep-water formation region, whereas global export production is controlled mainly by the biological pump and circulation in the Subantarctic intermediate and mode water formation region. The existence of this biogeochemical divide separating the Antarctic from the Subantarctic suggests that it may be possible for climate change or human intervention to modify one of these without greatly altering the other.     

Glacial--interglacial stability of ocean pH inferred from foraminifer dissolution rates

The pH of the ocean is controlled by the chemistry of calcium carbonate. This system in turn plays a large role in regulating the CO2 concentration of the atmosphere on timescales of thousands of years and longer. Reconstructions of ocean pH and carbonate-ion concentration are therefore needed to understand the ocean's role in the global carbon cycle. During the Last Glacial Maximum (LGM), the pH of the whole ocean is thought to have been significantly more basic, as inferred from the isotopic composition of boron incorporated into calcium carbonate shells, which would partially explain the lower atmospheric CO2 concentration at that time. Here we reconstruct carbonate-ion concentration--and hence pH--of the glacial oceans, using the extent of calcium carbonate dissolution observed in foraminifer faunal assemblages as compiled in the extensive global CLIMAP data set. We observe decreased carbonate-ion concentrations in the glacial Atlantic Ocean, by roughly 20 micromolkg-1, while little change occurred in the Indian and Pacific oceans relative to today. In the Pacific Ocean, a small (5 micromolkg-1) increase occurred below 3,000m. This rearrangement of ocean pH may be due to changing ocean circulation from glacial to present times, but overall we see no evidence for a shift in the whole-ocean pH as previously inferred from boron isotopes.     

Increased thermohaline stratification as a possible cause for an ocean anoxic event in the Cretaceous period

Ocean anoxic events were periods of high carbon burial that led to drawdown of atmospheric carbon dioxide, lowering of bottom-water oxygen concentrations and, in many cases, significant biological extinction. Most ocean anoxic events are thought to be caused by high productivity and export of carbon from surface waters which is then preserved in organic-rich sediments, known as black shales. But the factors that triggered some of these events remain uncertain. Here we present stable isotope data from a mid-Cretaceous ocean anoxic event that occurred 112 Myr ago, and that point to increased thermohaline stratification as the probable cause. Ocean anoxic event 1b is associated with an increase in surface-water temperatures and runoff that led to decreased bottom-water formation and elevated carbon burial in the restricted basins of the western Tethys and North Atlantic. This event is in many ways similar to that which led to the more recent Plio-Pleistocene Mediterranean sapropels, but the greater geographical extent and longer duration (approximately 46 kyr) of ocean anoxic event 1b suggest that processes leading to such ocean anoxic events in the North Atlantic and western Tethys were able to act over a much larger region, and sequester far more carbon, than any of the Quaternary sapropels.     

Effect of trace metal availability on coccolithophorid calcification

The deposition of atmospheric dust into the ocean has varied considerably over geological time. Because some of the trace metals contained in dust are essential plant nutrients which can limit phytoplankton growth in parts of the ocean, it has been suggested that variations in dust supply to the surface ocean might influence primary production. Whereas the role of trace metal availability in photosynthetic carbon fixation has received considerable attention, its effect on biogenic calcification is virtually unknown. The production of both particulate organic carbon and calcium carbonate (CaCO3) drives the ocean's biological carbon pump. The ratio of particulate organic carbon to CaCO3 export, the so-called rain ratio, is one of the factors determining CO2 sequestration in the deep ocean. Here we investigate the influence of the essential trace metals iron and zinc on the prominent CaCO3-producing microalga Emiliania huxleyi. We show that whereas at low iron concentrations growth and calcification are equally reduced, low zinc concentrations result in a de-coupling of the two processes. Despite the reduced growth rate of zinc-limited cells, CaCO3 production rates per cell remain unaffected, thus leading to highly calcified cells. These results suggest that changes in dust deposition can affect biogenic calcification in oceanic regions characterized by trace metal limitation, with possible consequences for CO2 partitioning between the atmosphere and the ocean.     

Reduced nitrogen fixation in the glacial ocean inferred from changes in marine nitrogen and phosphorus inventories.

To explain the lower atmospheric CO2 concentrations during glacial periods, it has been suggested that the productivity of marine phytoplankton was stimulated by an increased flux of iron-bearing dust to the oceans. One component of this theory is that iron-an essential element/nutrient for nitrogen-fixing organisms-will increase the rate of marine nitrogen fixation, fuelling the growth of other marine phytoplankton and increasing CO2 uptake. Here we present data that questions this hypothesis. From a sediment core off the northwestern continental margin of Mexico, we show that denitrification and phosphorite formation-processes that occur in oxygen-deficient upwelling regions, removing respectively nitrogen and phosphorus from the ocean-declined in glacial periods, thus increasing marine inventories of nitrogen and phosphorus. But increases in phosphorus were smaller and less rapid, leading to increased N/P ratios in the oceans. Acknowledging that phytoplankton require nitrogen and phosphorus in constant proportions, the Redfield ratio, and that N/P ratios greater than the Redfield ratio are likely to suppress nitrogen fixation, we suggest therefore that marine productivity did not increase in glacial periods in response to either increased nutrient inventories or greater iron supply.     

Atlantic overturning responses to Late Pleistocene climate forcings

The factors driving glacial changes in ocean overturning circulation are not well understood. On the basis of a comparison of 20 climate variables over the past four glacial cycles, the SPECMAP project proposed that summer insolation at high northern latitudes (that is, Milankovitch forcing) drives the same sequence of ocean circulation and other climate responses over 100-kyr eccentricity cycles, 41-kyr obliquity cycles and 23-kyr precession cycles. SPECMAP analysed the circulation response at only a few sites in the Atlantic Ocean, however, and the phase of circulation response has been shown to vary by site and orbital band. Here we test the SPECMAP hypothesis by measuring the phase of orbital responses in benthic delta(13)C (a proxy indicator of ocean nutrient content) at 24 sites throughout the Atlantic over the past 425 kyr. On the basis of delta(13)C responses at 3,000-4,010 m water depth, we find that maxima in Milankovitch forcing are associated with greater mid-depth overturning in the obliquity band but less overturning in the precession band. This suggests that Atlantic overturning is strongly sensitive to factors beyond ice volume and summer insolation at high northern latitudes. A better understanding of these processes could lead to improvements in model estimates of overturning rates, which range from a 40 per cent increase to a 40 per cent decrease at the Last Glacial Maximum and a 10-50 per cent decrease over the next 140 yr in response to projected increases in atmospheric CO(2) (ref. 4).     

North Pacific seasonality and the glaciation of North America 2.7 million years ago

In the context of gradual Cenozoic cooling, the timing of the onset of significant Northern Hemisphere glaciation 2.7 million years ago is consistent with Milankovitch's orbital theory, which posited that ice sheets grow when polar summertime insolation and temperature are low. However, the role of moisture supply in the initiation of large Northern Hemisphere ice sheets has remained unclear. The subarctic Pacific Ocean represents a significant source of water vapour to boreal North America, but it has been largely overlooked in efforts to explain Northern Hemisphere glaciation. Here we present alkenone unsaturation ratios and diatom oxygen isotope ratios from a sediment core in the western subarctic Pacific Ocean, indicating that 2.7 million years ago late-summer sea surface temperatures in this ocean region rose in response to an increase in stratification. At the same time, winter sea surface temperatures cooled, winter floating ice became more abundant and global climate descended into glacial conditions. We suggest that the observed summer warming extended into the autumn, providing water vapour to northern North America, where it precipitated and accumulated as snow, and thus allowed the initiation of Northern Hemisphere glaciation.     

Orbitally induced oscillations in the East Antarctic ice sheet at the Oligocene/Miocene boundary

Between 34 and 15 million years (Myr) ago, when planetary temperatures were 3-4 degrees C warmer than at present and atmospheric CO2 concentrations were twice as high as today, the Antarctic ice sheets may have been unstable. Oxygen isotope records from deep-sea sediment cores suggest that during this time fluctuations in global temperatures and high-latitude continental ice volumes were influenced by orbital cycles. But it has hitherto not been possible to calibrate the inferred changes in ice volume with direct evidence for oscillations of the Antarctic ice sheets. Here we present sediment data from shallow marine cores in the western Ross Sea that exhibit well dated cyclic variations, and which link the extent of the East Antarctic ice sheet directly to orbital cycles during the Oligocene/Miocene transition (24.1-23.7 Myr ago). Three rapidly deposited glacimarine sequences are constrained to a period of less than 450 kyr by our age model, suggesting that orbital influences at the frequencies of obliquity (40 kyr) and eccentricity (125 kyr) controlled the oscillations of the ice margin at that time. An erosional hiatus covering 250 kyr provides direct evidence for a major episode of global cooling and ice-sheet expansion about 23.7 Myr ago, which had previously been inferred from oxygen isotope data (Mi1 event).