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.     

Evidence against dust-mediated control of glacial-interglacial changes in atmospheric CO2

The low concentration of atmospheric CO2 inferred to have been present during glacial periods is thought to have been partly caused by an increased supply of iron-bearing dust to the ocean surface. This is supported by a recent model that attributes half of the CO2 reduction during past glacial stages to iron-stimulated uptake of CO2 by phytoplankton in the Southern Ocean. But atmospheric dust fluxes to the Southern Ocean, even in glacial periods, are thought to be relatively low and therefore it has been proposed that Southern Ocean productivity might be influenced by iron deposited elsewhere-for example, in the Northern Hemisphere-which is then transported south via ocean circulation (similar to the distal supply of iron to the equatorial Pacific Ocean). Here we examine the timing of dust fluxes to the North Atlantic Ocean, in relation to climate records from the Vostok ice core in Antarctica around the time of the penultimate deglaciation (about 130 kyr ago). Two main dust peaks occurred 155 kyr and 130 kyr ago, but neither was associated with the CO2 rise recorded in the Vostok ice core. This mismatch, together with the low dust flux supplied to the Southern Ocean, suggests that dust-mediated iron fertilization of the Southern Ocean did not significantly influence atmospheric CO2 at the termination of the penultimate glaciation.     

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.     

Ocean nutrient ratios governed by plankton biogeography

The major nutrients nitrate and phosphate have one of the strongest correlations in the sea, with a slope similar to the average nitrogen (N) to phosphorus (P) content of plankton biomass (N/P = 16:1). The processes through which this global relationship emerges despite the wide range of N/P ratios at the organism level are not known. Here we use an ocean circulation model and observed nutrient distributions to show that the N/P ratio of biological nutrient removal varies across latitude in Southern Ocean surface waters, from 12:1 in the polar ocean to 20:1 in the sub-Antarctic zone. These variations are governed by regional differences in the species composition of the plankton community. The covariation of dissolved nitrate and phosphate is maintained by ocean circulation, which mixes the shallow subsurface nutrients between distinct biogeographic provinces. Climate-driven shifts in these marine biomes may alter the mean N/P ratio and the associated carbon export by Southern Ocean ecosystems.     

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.     

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.     

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.     

Dual modes of the carbon cycle since the Last Glacial Maximum

The most conspicuous feature of the record of past climate contained in polar ice is the rapid warming which occurs after long intervals of gradual cooling. During the last four transitions from glacial to interglacial conditions, over which such abrupt warmings occur, ice records indicate that the CO2 concentration of the atmosphere increased by roughly 80 to 100 parts per million by volume. But the causes of the atmospheric CO2 concentration increases are unclear. Here we present the stable-carbon-isotope composition (delta 13 CO2) of CO2 extracted from air trapped in ice at Taylor Dome, Antarctica, from the Last Glacial Maximum to the onset of Holocene times. The global carbon cycle is shown to have operated in two distinct primary modes on the timescale of thousands of years, one when climate was changing relatively slowly and another when warming was rapid, each with a characteristic average stable-carbon-isotope composition of the net CO2 exchanged by the atmosphere with the land and oceans. delta 13 CO2 increased between 16.5 and 9 thousand years ago by slightly more than would be estimated to be caused by the physical effects of a 5 degrees C rise in global average sea surface temperature driving a CO2 efflux from the ocean, but our data do not allow specific causes to be constrained.     

The evolution of the marine phosphate reservoir

Phosphorus is a biolimiting nutrient that has an important role in regulating the burial of organic matter and the redox state of the ocean-atmosphere system. The ratio of phosphorus to iron in iron-oxide-rich sedimentary rocks can be used to track dissolved phosphate concentrations if the dissolved silica concentration of sea water is estimated. Here we present iron and phosphorus concentration ratios from distal hydrothermal sediments and iron formations through time to study the evolution of the marine phosphate reservoir. The data suggest that phosphate concentrations have been relatively constant over the Phanerozoic eon, the past 542 million years (Myr) of Earth's history. In contrast, phosphate concentrations seem to have been elevated in Precambrian oceans. Specifically, there is a peak in phosphorus-to-iron ratios in Neoproterozoic iron formations dating from ～750 to ～635?Myr ago, indicating unusually high dissolved phosphate concentrations in the aftermath of widespread, low-latitude 'snowball Earth' glaciations. An enhanced postglacial phosphate flux would have caused high rates of primary productivity and organic carbon burial and a transition to more oxidizing conditions in the ocean and atmosphere. The snowball Earth glaciations and Neoproterozoic oxidation are both suggested as triggers for the evolution and radiation of metazoans. We propose that these two factors are intimately linked; a glacially induced nutrient surplus could have led to an increase in atmospheric oxygen, paving the way for the rise of metazoan life.     

Rapid and early export of Phaeocystis antarctica blooms in the Ross Sea, Antarctica

The Southern Ocean is very important for the potential sequestration of carbon dioxide in the oceans and is expected to be vulnerable to changes in carbon export forced by anthropogenic climate warming. Annual phytoplankton blooms in seasonal ice zones are highly productive and are thought to contribute significantly to pCO2 drawdown in the Southern Ocean. Diatoms are assumed to be the most important phytoplankton class with respect to export production in the Southern Ocean; however, the colonial prymnesiophyte Phaeocystis antarctica regularly forms huge blooms in seasonal ice zones and coastal Antarctic waters. There is little evidence regarding the fate of carbon produced by P. antarctica in the Southern Ocean, although remineralization in the upper water column has been proposed to be the main pathway in polar waters. Here we present evidence for early and rapid carbon export from P. antarctica blooms to deep water and sediments in the Ross Sea. Carbon sequestration from P. antarctica blooms may influence the carbon cycle in the Southern Ocean, especially if projected climatic changes lead to an alteration in the structure of the phytoplankton community.     

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.     

Stable sea surface temperatures in the western Pacific warm pool over the past 1.75 million years

About 850,000 years ago, the period of the glacial cycles changed from 41,000 to 100,000 years. This mid-Pleistocene climate transition has been attributed to global cooling, possibly caused by a decrease in atmospheric carbon dioxide concentrations. However, evidence for such cooling is currently restricted to the cool upwelling regions in the eastern equatorial oceans, although the tropical warm pools on the western side of the ocean basins are particularly sensitive to changes in radiative forcing. Here we present high-resolution records of sea surface temperatures spanning the past 1.75 million years, obtained from oxygen isotopes and Mg/Ca ratios in planktonic foraminifera from the western Pacific warm pool. In contrast with the eastern equatorial regions, sea surface temperatures in the western Pacific warm pool are relatively stable throughout the Pleistocene epoch, implying little long-term change in the tropical net radiation budget. Our results challenge the hypothesis of a gradual decrease in atmospheric carbon dioxide concentrations as a dominant trigger of the longer glacial cycles since 850,000 years ago. Instead, we infer that the temperature contrast across the equatorial Pacific Ocean increased, which might have had a significant influence on the mid-Pleistocene climate transition.     

Negligible glacial-interglacial variation in continental chemical weathering rates

Chemical weathering of the continents is central to the regulation of atmospheric carbon dioxide concentrations, and hence global climate. On million-year timescales silicate weathering leads to the draw-down of carbon dioxide, and on millennial timescales chemical weathering affects the calcium carbonate saturation state of the oceans and hence their uptake of carbon dioxide. However, variations in chemical weathering rates over glacial-interglacial cycles remain uncertain. During glacial periods, cold and dry conditions reduce the rate of chemical weathering, but intense physical weathering and the exposure of carbonates on continental shelves due to low sea levels may increase this rate. Here we present high-resolution records of the lead isotope composition of ferromanganese crusts from the North Atlantic Ocean that cover the past 550,000 years. Combining these records with a simple quantitative model of changes in the lead isotope composition of the deep North Atlantic Ocean in response to chemical weathering, we find that chemical weathering rates were two to three times lower in the glaciated interior of the North Atlantic Region during glacial periods than during the intervening interglacial periods. This decrease roughly balances the increase in chemical weathering caused by the exposure of continental shelves, indicating that chemical weathering rates remained relatively constant on glacial-interglacial timescales. On timescales of more than a million years, however, we suggest that enhanced weathering of silicate glacial sediments during interglacial periods results in a net draw-down of atmospheric carbon dioxide, creating a positive feedback on global climate that, once initiated, promotes cooling and further glaciation.     

Marine control of biological production in the eastern equatorial Pacific Ocean

The eastern equatorial Pacific Ocean is the site of approximately 20-50% of new biological production in the global oceans. This region is also responsible for the greatest efflux of CO2 from oceans to the atmosphere. New production, which fixes carbon in response to external inputs of nutrients as opposed to supply from local nutrient recycling, is thought to modulate the CO2 release. But what controls new production in this region is less clear. Here we present a quantitative reconstruction of biological production in the surface ocean for this region over the past 130,000 years, which shows that the equatorial Pacific Ocean exhibits higher-frequency variations than the South Equatorial Current. Comparison of these records with palaeotemperature reconstructions indicates that atmospherically driven mechanisms--such as aeolian flux of iron or wind-driven changes in upwelling rate of nutrient-rich waters--are unlikely to have influenced longer-term rates of production in this region. Instead, biological production appears to be governed by changes in ocean circulation and the chemical composition of upwelled water.     

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.     

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.     

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.     

The influence of Antarctic sea ice on glacial-interglacial CO2 variations

Ice-core measurements indicate that atmospheric CO2 concentrations during glacial periods were consistently about 80 parts per million lower than during interglacial periods. Previous explanations for this observation have typically had difficulty accounting for either the estimated glacial O2 concentrations in the deep sea, 13C/12C ratios in Antarctic surface waters, or the depth of calcite saturation; also lacking is an explanation for the strong link between atmospheric CO2 and Antarctic air temperature. There is growing evidence that the amount of deep water upwelling at low latitudes is significantly overestimated in most ocean general circulation models and simpler box models previously used to investigate this problem. Here we use a box model with deep-water upwelling confined to south of 55 degrees S to investigate the glacial-interglacial linkages between Antarctic air temperature and atmospheric CO2 variations. We suggest that low glacial atmospheric CO2 levels might result from reduced deep-water ventilation associated with either year-round Antarctic sea-ice coverage, or wintertime coverage combined with ice-induced stratification during the summer. The model presented here reproduces 67 parts per million of the observed glacial-interglacial CO2 difference, as a result of reduced air-sea gas exchange in the Antarctic region, and is generally consistent with the additional observational constraints.     

Holocene Southern Ocean surface temperature variability west of the Antarctic Peninsula

The disintegration of ice shelves, reduced sea-ice and glacier extent, and shifting ecological zones observed around Antarctica highlight the impact of recent atmospheric and oceanic warming on the cryosphere. Observations and models suggest that oceanic and atmospheric temperature variations at Antarctica's margins affect global cryosphere stability, ocean circulation, sea levels and carbon cycling. In particular, recent climate changes on the Antarctic Peninsula have been dramatic, yet the Holocene climate variability of this region is largely unknown, limiting our ability to evaluate ongoing changes within the context of historical variability and underlying forcing mechanisms. Here we show that surface ocean temperatures at the continental margin of the western Antarctic Peninsula cooled by 3-4 °C over the past 12,000 years, tracking the Holocene decline of local (65° S) spring insolation. Our results, based on TEX(86) sea surface temperature (SST) proxy evidence from a marine sediment core, indicate the importance of regional summer duration as a driver of Antarctic seasonal sea-ice fluctuations. On millennial timescales, abrupt SST fluctuations of 2-4 °C coincide with globally recognized climate variability. Similarities between our SSTs, Southern Hemisphere westerly wind reconstructions and El Ni?o/Southern Oscillation variability indicate that present climate teleconnections between the tropical Pacific Ocean and the western Antarctic Peninsula strengthened late in the Holocene epoch. We conclude that during the Holocene, Southern Ocean temperatures at the western Antarctic Peninsula margin were tied to changes in the position of the westerlies, which have a critical role in global carbon cycling.     

Twenty-first-century warming of a large Antarctic ice-shelf cavity by a redirected coastal current

The Antarctic ice sheet loses mass at its fringes bordering the Southern Ocean. At this boundary, warm circumpolar water can override the continental slope front, reaching the grounding line through submarine glacial troughs and causing high rates of melting at the deep ice-shelf bases. The interplay between ocean currents and continental bathymetry is therefore likely to influence future rates of ice-mass loss. Here we show that a redirection of the coastal current into the Filchner Trough and underneath the Filchner-Ronne Ice Shelf during the second half of the twenty-first century would lead to increased movement of warm waters into the deep southern ice-shelf cavity. Water temperatures in the cavity would increase by more than 2 degrees Celsius and boost average basal melting from 0.2 metres, or 82 billion tonnes, per year to almost 4 metres, or 1,600 billion tonnes, per year. Our results, which are based on the output of a coupled ice-ocean model forced by a range of atmospheric outputs from the HadCM3 climate model, suggest that the changes would be caused primarily by an increase in ocean surface stress in the southeastern Weddell Sea due to thinning of the formerly consolidated sea-ice cover. The projected ice loss at the base of the Filchner-Ronne Ice Shelf represents 80 per cent of the present Antarctic surface mass balance. Thus, the quantification of basal mass loss under changing climate conditions is important for projections regarding the dynamics of Antarctic ice streams and ice shelves, and global sea level rise.