Reconciling ice core CO2 and land-use change following New World-Old World contact.

Ice core records of carbon dioxide (CO2) throughout the last 2000 years provide context for the unprecedented anthropogenic rise in atmospheric CO2 and insights into global carbon cycle dynamics. Yet the atmospheric history of CO2 remains uncertain in some time intervals. Here we present measurements of CO2 and methane (CH4) in the Skytrain ice core from 1450 to 1700 CE. Results suggest a sudden decrease in CO2 around 1610 CE in one widely used record may be an artefact of a small number of anomalously low values. Our analysis supports a more gradual decrease in CO2 of 0.5 ppm per decade from 1516 to 1670 CE, with an inferred land carbon sink of 2.6 PgC per decade. This corroborates modelled scenarios of large-scale reorganisation of land use in the Americas following New World-Old World contact, whereas a rapid decrease in CO2 at 1610 CE is incompatible with even the most extreme land-use change scenarios.

The Growth Response of Two Diatom Species to Atmospheric Dust from the Last Glacial Maximum.

Relief of iron (Fe) limitation in the surface Southern Ocean has been suggested as one driver of the regular glacial-interglacial cycles in atmospheric carbon dioxide (CO2). The proposed cause is enhanced deposition of Fe-bearing atmospheric dust to the oceans during glacial intervals, with consequent effects on export production and the carbon cycle. However, understanding the role of enhanced atmospheric Fe supply in biogeochemical cycles is limited by knowledge of the fluxes and 'bioavailability' of atmospheric Fe during glacial intervals. Here, we assess the effect of Fe fertilization by dust, dry-extracted from the Last Glacial Maximum portion of the EPICA Dome C Antarctic ice core, on the Antarctic diatom species Eucampia antarctica and Proboscia inermis. Both species showed strong but differing reactions to dust addition. E. antarctica increased cell number (3880 vs. 786 cells mL-1), chlorophyll a (51 vs. 3.9 µg mL-1) and particulate organic carbon (POC; 1.68 vs. 0.28 µg mL-1) production in response to dust compared to controls. P. inermis did not increase cell number in response to dust, but chlorophyll a and POC per cell both strongly increased compared to controls (39 vs. 15 and 2.13 vs. 0.95 ng cell-1 respectively). The net result of both responses was a greater production of POC and chlorophyll a, as well as decreased Si:C and Si:N incorporation ratios within cells. However, E, antarctica decreased silicate uptake for the same nitrate and carbon uptake, while P. inermis increased carbon and nitrate uptake for the same silicate uptake. This suggests that nutrient utilization changes in response to Fe addition could be driven by different underlying mechanisms between different diatom species. Enhanced supply of atmospheric dust to the surface ocean during glacial intervals could therefore have driven nutrient-utilization changes which could permit greater carbon fixation for lower silica utilization. Additionally, both species responded more strongly to lower amounts of direct Fe chloride addition than they did to dust, suggesting that not all the Fe released from dust was in a bioavailable form available for uptake by diatoms.

Ice sheets and nitrogen.

Snow and ice play their most important role in the nitrogen cycle as a barrier to land-atmosphere and ocean-atmosphere exchanges that would otherwise occur. The inventory of nitrogen compounds in the polar ice sheets is approximately 260 Tg N, dominated by nitrate in the much larger Antarctic ice sheet. Ice cores help to inform us about the natural variability of the nitrogen cycle at global and regional scale, and about the extent of disturbance in recent decades. Nitrous oxide concentrations have risen about 20 per cent in the last 200 years and are now almost certainly higher than at any time in the last 800 000 years. Nitrate concentrations recorded in Greenland ice rose by a factor of 2-3, particularly between the 1950s and 1980s, reflecting a major change in NOx emissions reaching the background atmosphere. Increases in ice cores drilled at lower latitudes can be used to validate or constrain regional emission inventories. Background ammonium concentrations in Greenland ice show no significant recent trend, although the record is very noisy, being dominated by spikes of input from biomass burning events. Neither nitrate nor ammonium shows significant recent trends in Antarctica, although their natural variations are of biogeochemical and atmospheric chemical interest. Finally, it has been found that photolysis of nitrate in the snowpack leads to significant re-emissions of NOx that can strongly impact the regional atmosphere in snow-covered areas.

Chemical signals of past climate and environment from polar ice cores and firn air.

Chemical and isotopic records obtained from polar ice cores have provided some of the most iconic datasets in Earth system science. Here, I discuss how the different records are formed in the ice sheets, emphasising in particular the contrast between chemistry held in the snow/ice phase, and that which is trapped in air bubbles. Air diffusing slowly through the upper firn layers of the ice sheet can also be sampled in large volumes to give more recent historical information on atmospheric composition. The chemical and geophysical issues that have to be solved to interpret ice core data in terms of atmospheric composition and emission changes are also highlighted. Ice cores and firn air have provided particularly strong evidence about recent changes (last few decades to centuries), including otherwise inaccessible data on increases in compounds that are active as greenhouse gases or as agents of stratospheric depletion. On longer timescales (up to 800,000 years in Antarctica), ice cores reveal major changes in biogeochemical cycling, which acted as feedbacks on the very major changes in climate between glacial and interglacial periods.

Antarctic accumulation seasonality.

The resemblance of the orbitally filtered isotope signal from the past 340 kyr in Antarctic ice cores to Northern Hemisphere summer insolation intensity has been used to suggest that the northern hemisphere may drive orbital-scale global climate changes. A recent Letter by Laepple et al. suggests that, contrary to this interpretation, this semblance may instead be explained by weighting the orbitally controlled Antarctic seasonal insolation cycle with a static (present-day) estimate of the seasonal cycle of accumulation. We suggest, however, that both time variability in accumulation seasonality and alternative stable seasonality can markedly alter the weighted insolation signal. This indicates that, if the last 340 kyr of Antarctic accumulation has not always looked like the estimate of precipitation and accumulation seasonality made by Laepple et al., this particular accumulation weighting explanation of the Antarctic orbital-scale isotopic signal might not be robust.

Greenhouse gases in the Earth system: a palaeoclimate perspective.

While the trends in greenhouse gas concentrations in recent decades are clear, their significance is only revealed when viewed in the context of a longer time period. Fortunately, the air bubbles in polar ice cores provide an unusually direct method of determining the concentrations of stable gases over a period of (so far) 800,000 years. Measurements on different cores with varying characteristics, as well as an overlap of ice-core and atmospheric measurements covering the same time period, show that the ice-core record provides a faithful record of changing atmospheric composition. The mixing ratio of CO(2) is now 30 per cent higher than any value observed in the ice-core record, while methane is more than double any observed value; the rate of change also appears extraordinary compared with natural changes. Before the period when anthropogenic changes have dominated, there are very interesting natural changes in concentration, particularly across glacial/interglacial cycles, and these can be used to understand feedbacks in the Earth system. The phasing of changes in temperature and CO(2) across glacial/interglacial transitions is consistent with the idea that CO(2) acts as an important amplifier of climate changes in the natural system. Even larger changes are inferred to have occurred in periods earlier than the ice cores cover, and these events might be used to constrain assessments of the way the Earth could respond to higher than present concentrations of CO(2), and to a large release of carbon: however, more certainty about CO(2) concentrations beyond the time period covered by ice cores is needed before such constraints can be fully realized.

Proxies and measurement techniques for mineral dust in Antarctic ice cores.

To improve quantitative interpretation of ice core aeolian dust records, a systematic methodological comparison was made. This involved methods for water-insoluble particle counting (Coulter counter and laser-sensing particle detector), soluble ion analysis (ion chromatography and continuous flow analysis), elemental analysis (inductively coupled plasma mass spectroscopy at pH 1 and after full acid digestion), and water-insoluble elemental analysis (proton induced X-ray emission). Antarctic ice core samples covering the last deglaciation from the EPICA Dome C (EDC) and the EPICA Dronning Maud Land (EDML) cores were used. All methods correlate very well among each other, but the ratios of glacial age to Holocene concentrations, which are typically a factor approximately 100, differ between the methods by up to a factor of 2 with insoluble particles showing the largest variability. The recovery of ICP-MS measurements depends on the digestion method and is differentfor different elements and during different climatic periods. EDC and EDML samples have similar dust composition, which suggests a common dust source or a common mixture of sources for the two sites. The analyzed samples further reveal a change of dust composition during the last deglaciation.

SEM studies of the morphology and chemistry of polar ice.

Determining the microphysical location of impurities in natural ice from the polar regions is necessary for understanding the physical properties of ice and for assuring the integrity of ice core records. SEM, using a cold stage and X-ray microanalytical techniques, has proved to be the most powerful method so far for undertaking such work. Methods are adapted from those used to study frozen hydrated biological material. Sublimation within the cryo-chamber is often needed in order to concentrate impurities onto a plane, but this can lead to artifacts that must be recognized. Over 100 samples from different depths and sites in Greenland and Antarctica have been examined. Typical physical features, including air bubbles, clathrate hydrates of air, and dust particles are identified. The dust is found preferentially at grain boundaries in some samples; by pinning the boundaries, it can slow grain growth. Of the soluble material, chloride seems to be found most frequently in the ice lattice. Other impurities are found at grain boundaries, and only when the bulk concentration exceeds a threshold, at triple junctions. These findings give new insights into processes determining the physical properties of ice samples and of ice sheets, and new impetus for theoretical studies of the energetics that lead to this distribution.

Short-term variations in the occurrence of heavy metals in Antarctic snow from Coats Land since the 1920s.

Short-term variations in heavy metals concentrations in Antarctic snow have been investigated by analysing 13 metals (Al, V, Cr, Mn, Co, Cu, Zn, Ag, Cd, Ba, Pb, Bi and U) in a series of ultraclean samples collected from two snow pits in Coats Land in the Atlantic sector of Antarctica. The samples covered a approximately 70 years time period from the 1920s to 1990. They were analysed by inductively coupled plasma sector field mass spectrometry and graphite furnace atomic absorption spectrometry. The results conclusively show that there is a pronounced short-term (intra- and inter-annual) variability of heavy metal in Antarctic snow, with the highest concentrations being up to 100 times higher than the lowest ones for metal such as Cr, Mn, Pb and U. Contributions from the different possible natural and anthropogenic sources are found to be extremely variable. This is especially due to the large variability in the transport patterns of heavy metals from Southern America, Southern Africa and Australia to the Antarctic continent. Inputs from several volcanic events were identified in our samples from non-seasalt sulfate concentrations profiles. The only ones that gave clear signals for heavy metals were eruptions at Deception Island the proximity of which allowed for tropospheric transport to Coats Land.