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Abstract: The stable carbon isotopic signature of carbon dioxide (δ13CO2) measured in the air occlusions of polar ice provides important constraints on the carbon cycle in past climates. In order to exploit this information for previous glacial periods, one must use deep, clathrated ice, where the occluded air is preserved not in bubbles but in the form of air hydrates. Therefore, it must be established whether the original atmospheric δ13CO2 signature can be reconstructed from clathrated ice. We present a comparative study using coeval bubbly ice from Berkner Island and ice from the bubble–clathrate transformation zone (BCTZ) of EPICA Dome C (EDC). In the EDC samples the gas is partitioned into clathrates and remaining bubbles as shown by erroneously low and scattered CO2 concentration values, presenting a worst-case test for δ13CO2 reconstructions. Even so, the reconstructed atmospheric δ13CO2 values show only slightly larger scatter. The difference to data from coeval bubbly ice is statistically significant. However, the 0.16‰ magnitude of the offset is small for practical purposes, especially in light of uncertainty from non-uniform corrections for diffusion related fractionation that could contribute to the discrepancy. Our results are promising for palaeo-atmospheric studies of δ13CO2 using a ball mill dry extraction technique below the BCTZ of ice cores, where gas is not subject to fractionation into microfractures and between clathrate and bubble reservoirs. [Copyright &y& Elsevier]

The temperature increase at Vostok (Antarctica) from the last glacial maximum to the present warm period is about 8°C based on the deuterium isotope profile. The bore hole temperature (temperature profile in the ice sheet) indicates that the temperature difference may have been much larger, about 15°C. The temperature dependent gas occlusion process is the key to evaluate the two scenarios. Atmospheric air penetrates the porous firn layer of the ice sheet and gets trapped at the firn ice boundary. Consequently the air is younger than the surrounding ice when it gets enclosed in bubbles. This age difference (Δage) between ice and enclosed gas is temperature and accumulation rate dependent. Therefore it is possible to estimate paleotemperatures from a known Δage. We use the linkage between chronologies of CH4 and water isotopes from Byrd station and Vostok to obtain an experimental Δage for Vostok. This experimental Δage is then compared to modeled Δage for the two temperature scenarios. Our results indicate that the temperature reconstruction deduced from the water isotopic composition is the more probable one. [Copyright &y& Elsevier]

Atmospheric methane (CH4) records reconstructed from polar ice cores represent an integrated view on processes predominantly taking place in the terrestrial biogeosphere. Here, we present dual stable isotopic methane records [δ13CH4 and δD(CH4)] from four Antarctic ice cores, which provide improved constraints on past changes in natural methane sources. Our isotope data show that tropical wetlands and seasonally inundated floodplains are most likely the controlling sources of atmospheric methane variations for the current and two older interglacials and their preceding glacial maxima. The changes in these sources are steered by variations in temperature, precipitation, and the water table as modulated by insolation, (local) sea level, and monsoon intensity. Based on our δD(CH4) constraint, it seems that geologic emissions of methane may play a steady but only minor role in atmospheric CH4 changes and that the glacial budget is not dominated by these sources. Superimposed on the glacial/interglacial variations is a marked difference in both isotope records, with systematically higher values during the last 25,000 y compared with older time periods. This shift cannot be explained by climatic changes. Rather, our isotopic methane budget points to a marked increase in fire activity, possibly caused by biome changes and accumulation of fuel related to the late Pleistocene megafauna extinction, which took place in the course of the last glacial. [ABSTRACT FROM AUTHOR]

Abstract: Ancient air trapped inside bubbles in ice cores can now be analysed for methane concentration utilising a laser spectrometer coupled to a continuous melter system. We present a new ultra-high resolution record of atmospheric methane variability over the last 1800yr obtained from continuous analysis of a shallow ice core from the North Greenland Eemian project (NEEM-2011-S1) during a 4-week laboratory-based measurement campaign. Our record faithfully replicates the form and amplitudes of multi-decadal oscillations previously observed in other ice cores and demonstrates the detailed depth resolution (5.3cm), rapid acquisition time (30mday−1) and good long-term reproducibility (2.6%, 2σ) of the continuous measurement technique. In addition, we report the detection of high frequency ice core methane signals of non-atmospheric origin. Firstly, measurements of air from the firn–ice transition region and an interval of ice core dating from 1546–1560 AD (gas age) resolve apparently quasi-annual scale methane oscillations. Traditional gas chromatography measurements on discrete ice samples confirm these signals and indicate peak-to-peak amplitudes of ca. 22 parts per billion (ppb). We hypothesise that these oscillations result from staggered bubble close-off between seasonal layers of contrasting density during time periods of sustained multi-year atmospheric methane change. Secondly, we report the detection of abrupt (20–100cm depth interval), high amplitude (35–80ppb excess) methane spikes in the NEEM ice that are reproduced by discrete measurements. We show for the first time that methane spikes present in thin and infrequent layers in polar, glacial ice are accompanied by elevated concentrations of carbon- and nitrogen-based chemical impurities, and suggest that biological in-situ production may be responsible. [Copyright &y& Elsevier]

Abstract: In relation to Arctic warming, the possible occurrence of methane hydrate degassing events has attracted an increasing interest in recent years. We evaluate the atmospheric impact of rapid and massive emissions of methane and how they are imprinted in ice core records, by combining for the first time models of atmospheric chemistry and trace gas transport in firn. Different emission characteristics as well as climatic conditions (present, pre-industrial, glacial) are considered. The isotopic signatures characterizing stable isotopologues of methane DCH3 and 13CH4 are also analysed. Our results suggest little effect of clathrate degassing on the main methane oxidant: OH radicals. Due to the relatively short atmospheric lifetime of methane, the simulated clathrate-induced perturbations last for less than a century. This time scale is comparable to or shorter than the duration of air bubble closure in polar ice sheets. As a consequence, rapid methane perturbations in the atmosphere are strongly smoothed in ice core records. This smoothing mostly depends on the snow accumulation rate at the site of ice core drilling. We propose a methodology to identify a potential clathrate degassing event in ice core records. Continuous CH4 records from high accumulation rate sites could allow to decipher short time scale events. of CH4 should reveal a typical “lying S” shape at high accumulation rate sites, reflecting the combined effects of the clathrate source signature (negative excursion) and subsequent OH fractionation in the atmosphere (positive excursion). The amplitude ratio of the negative and positive swings recorded in Greenland and Antarctica under similar accumulation rate conditions could also indicate the latitude of a clathrate degassing event. [Copyright &y& Elsevier]