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Carbon monoxide (CO) is a naturally occurring atmospheric trace gas, a regulated pollutant, and one of the main components determining the oxidative capacity of the atmosphere. Evaluating climate–chemistry models under different conditions than today and constraining past CO sources requires a reliable record of atmospheric CO mixing ratios ([CO]) that includes data since preindustrial times. Here, we report the first continuous record of atmospheric [CO] for Southern Hemisphere (SH) high latitudes over the past 3 millennia. Our continuous record is a composite of three high-resolution Antarctic ice core gas records and firn air measurements from seven Antarctic locations. The ice core gas [CO] records were measured by continuous flow analysis (CFA), using an optical feedback cavity-enhanced absorption spectrometer (OF-CEAS), achieving excellent external precision (2.8–8.8 ppb; 2σ) and consistently low blanks (ranging from 4.1±1.2 to 7.4±1.4 ppb), thus enabling paleo-atmospheric interpretations. Six new firn air [CO] Antarctic datasets collected between 1993 and 2016 CE at the DE08-2, DSSW19K, DSSW20K, South Pole, Aurora Basin North (ABN), and Lock-In sites (and one previously published firn CO dataset at Berkner) were used to reconstruct the atmospheric history of CO from ∼1897 CE, using inverse modeling that incorporates the influence of gas transport in firn. Excellent consistency was observed between the youngest ice core gas [CO] and the [CO] from the base of the firn and between the recent firn [CO] and atmospheric [CO] measurements at Mawson station (eastern Antarctica), yielding a consistent and contiguous record of CO across these different archives. Our Antarctic [CO] record is relatively stable from -835 to 1500 CE, with mixing ratios within a 30–45 ppb range (2 σ). There is a ∼5 ppb decrease in [CO] to a minimum at around 1700 CE during the Little Ice Age. CO mixing ratios then increase over time to reach a maximum of ∼54 ppb by ∼1985 CE. Most of the industrial period [CO] growth occurred between about 1940 to 1985 CE, after which there was an overall [CO] decrease, as observed in Greenland firn air and later at atmospheric monitoring sites and attributed partly to reduced CO emissions from combustion sources. Our Antarctic ice core gas CO observations differ from previously published records in two key aspects. First, our mixing ratios are significantly lower than reported previously, suggesting that previous studies underestimated blank contributions. Second, our new CO record does not show a maximum in the late 1800s. The absence of a [CO] peak around the turn of the century argues against there being a peak in Southern Hemisphere biomass burning at this time, which is in agreement with (i) other paleofire proxies such as ethane or acetylene and (ii) conclusions reached by paleofire modeling. The combined ice core and firn air [CO] history, spanning -835 to 1992 CE, extended to the present by the Mawson atmospheric record, provides a useful benchmark for future atmospheric chemistry modeling studies. [ABSTRACT FROM AUTHOR]

The temperature of the Earth is one of the most important climate parameters. Proxy records of past climate changes, in particular temperature, represent a fundamental tool for exploring internal climate processes and natural climate forcings. Despite the excellent information provided by ice core records in Antarctica, the temperature variability of the past 2000 years is difficult to evaluate from the low-accumulation sites in the Antarctic continent interior. Here we present the results from the Aurora Basin North (ABN) ice core (71 ∘ S, 111 ∘ E, 2690 m a.s.l.) in the lower part of the East Antarctic plateau, where accumulation is substantially higher than other ice core drilling sites on the plateau, and provide unprecedented insight into East Antarctic past temperature variability. We reconstructed the temperature of the last 2000 years using two independent methods: the widely used water stable isotopes (δ18 O) and by inverse modelling of borehole temperature and past temperature gradients estimated from the inert gas stable isotopes (δ40 Ar and δ15 N). This second reconstruction is based on three independent measurement types: borehole temperature, firn thickness, and firn temperature gradient. The δ18 O temperature reconstruction supports stable temperature conditions within 1 ∘ C over the past 2000 years, in agreement with other ice core δ18 O records in the region. However, the gas and borehole temperature reconstruction suggests that surface conditions 2 ∘ C cooler than average prevailed in the 1000–1400 CE period and supports a 20th century warming of 1 ∘ C. A precipitation hiatus during cold periods could explain why water isotope temperature reconstruction underestimates the temperature changes. Both reconstructions arguably record climate in their own way, with a focus on atmospheric and hydrologic cycles for water isotopes, as opposed to surface temperature for gas isotopes and boreholes. This study demonstrates the importance of using a variety of sources for comprehensive paleoclimate reconstructions. [ABSTRACT FROM AUTHOR]

Carbon monoxide (CO) is a regulated pollutant and one of the key components determining the oxidizing capacity of the atmosphere. Obtaining a reliable record of atmospheric CO mixing ratios ([CO]) since preindustrial times is necessary to evaluate climate–chemistry models under conditions different from today and to constrain past CO sources. We present high-resolution measurements of CO mixing ratios from ice cores drilled at five different sites on the Greenland ice sheet that experience a range of snow accumulation rates, mean surface temperatures, and different chemical compositions. An optical-feedback cavity-enhanced absorption spectrometer (OF-CEAS) was coupled with continuous melter systems and operated during four analytical campaigns conducted between 2013 and 2019. Overall, continuous flow analysis (CFA) of CO was carried out on over 700 m of ice. The CFA-based CO measurements exhibit excellent external precision (ranging from 3.3 to 6.6 ppbv , 1 σ) and achieve consistently low blanks (ranging from 4.1±1.2 to 12.6±4.4 ppbv), enabling paleoatmospheric interpretations. However, the five CO records all exhibit variability that is too large and rapid to reflect past atmospheric mixing ratio changes. Complementary tests conducted on discrete ice samples demonstrate that these variations are not artifacts of the analytical method (i.e., production of CO from organics in the ice during melting) but are very likely related to in situ CO production within the ice before analysis. Evaluation of the signal resolution and co-investigation of high-resolution records of CO and total organic carbon (TOC) suggest that past atmospheric CO variations can be extracted from the records' baselines with accumulation rates higher than 20 cm w.e.yr-1 (water equivalent per year). Consistent baseline CO records from four Greenland sites are combined to produce a multisite average ice core reconstruction of past atmospheric CO for the Northern Hemisphere high latitudes, covering the period from 1700 to 1957 CE. Such a reconstruction should be taken as an upper bound of past atmospheric CO abundance. From 1700 to 1875 CE, the record reveals stable or slightly increasing values in the 100–115 ppbv range. From 1875 to 1957 CE, the record indicates a monotonic increase from 114±4 to 147±6 ppbv. The ice core multisite CO record exhibits an excellent overlap with the atmospheric CO record from Greenland firn air which spans the 1950–2010 CE time period. The combined ice core and firn air CO history, spanning 1700–2010 CE, provides useful constraints for future model studies of atmospheric changes since the preindustrial period. [ABSTRACT FROM AUTHOR]

Deglaciations are characterized by the largest natural changes in methane (CH 4) and nitrous oxide (N 2 O) concentrations of the past 800 000 years. Reconstructions of millennial- to centennial-scale variability within these periods are mostly restricted to the last deglaciation. In this study, we present composite records of CH 4 and N 2 O concentrations from the EPICA Dome C ice core covering the penultimate deglaciation at temporal resolutions of ∼100 years. Our data permit the identification of centennial-scale fluctuations during the transition from glacial to interglacial levels. At ∼134000 and ∼129000 years before present (hereafter ka), both CH 4 and N 2 O increased on centennial timescales. These abrupt rises are similar to the fluctuations associated with the Dansgaard–Oeschger events identified in the last glacial period. In addition, gradually rising N 2 O levels at ∼130 ka resemble a pattern of increasing N 2 O concentrations on millennial timescales characterizing the later part of Heinrich stadials. Overall, the events in CH 4 and N 2 O during the penultimate deglaciation exhibit modes of variability that are also found during the last deglaciation and glacial cycle, suggesting that the processes leading to changes in emission during the transitions were similar but their timing differed. [ABSTRACT FROM AUTHOR]

Using new and previously published CO2 data from the EPICA Dome C ice core (EDC), we reconstruct a new high-resolution record of atmospheric CO2 during Marine Isotope Stage (MIS) 6 (190 to 135 ka) the penultimate glacial period. Similar to the last glacial cycle, where high-resolution data already exists, our record shows that during longer North Atlantic (NA) stadials, millennial CO2 variations during MIS 6 are clearly coincident with the bipolar seesaw signal in the Antarctic temperature record. However, during one short stadial in the NA, atmospheric CO2 variation is small (∼5 ppm) and the relationship between temperature variations in EDC and atmospheric CO2 is unclear. The magnitude of CO2 increase during Carbon Dioxide Maxima (CDM) is closely related to the NA stadial duration in both MIS 6 and MIS 3 (60–27 ka). This observation implies that during the last two glacials the overall bipolar seesaw coupling of climate and atmospheric CO2 operated similarly. In addition, similar to the last glacial period, CDM during the earliest MIS 6 show different lags with respect to the corresponding abrupt CH4 rises, the latter reflecting rapid warming in the Northern Hemisphere (NH). During MIS 6i at around 181.5± 0.3 ka, CDM 6i lags the abrupt warming in the NH by only 240± 320 years. However, during CDM 6iv (171.1± 0.2 ka) and CDM 6iii (175.4± 0.4 ka) the lag is much longer: 1290± 540 years on average. We speculate that the size of this lag may be related to a larger expansion of carbon-rich, southern-sourced waters into the Northern Hemisphere in MIS 6, providing a larger carbon reservoir that requires more time to be depleted. [ABSTRACT FROM AUTHOR]

We measured the methane mixing ratios of enclosed air in five ice core sections drilled on the East Antarctic Plateau. Our work aims to study two effects that alter the recorded gas concentrations in ice cores: layered gas trapping artifacts and firn smoothing. Layered gas trapping artifacts are due to the heterogeneous nature of polar firn, where some strata might close early and trap abnormally old gases that appear as spurious values during measurements. The smoothing is due to the combined effects of diffusive mixing in the firn and the progressive closure of bubbles at the bottom of the firn. Consequently, the gases trapped in a given ice layer span a distribution of ages. This means that the gas concentration in an ice layer is the average value over a certain period of time, which removes the fast variability from the record. Here, we focus on the study of East Antarctic Plateau ice cores, as these low-accumulation ice cores are particularly affected by both layering and smoothing. We use high-resolution methane data to test a simple trapping model reproducing the layered gas trapping artifacts for different accumulation conditions typical of the East Antarctic Plateau. We also use the high-resolution methane measurements to estimate the gas age distributions of the enclosed air in the five newly measured ice core sections. It appears that for accumulations below 2 cmiceequivalentyr-1 the gas records experience nearly the same degree of smoothing. We therefore propose to use a single gas age distribution to represent the firn smoothing observed in the glacial ice cores of the East Antarctic Plateau. Finally, we used the layered gas trapping model and the estimation of glacial firn smoothing to quantify their potential impacts on a hypothetical 1.5-million-year-old ice core from the East Antarctic Plateau. Our results indicate that layering artifacts are no longer individually resolved in the case of very thinned ice near the bedrock. They nonetheless contribute to slight biases of the measured signal (less than 10 ppbv and 0.5 ppmv in the case of methane using our currently established continuous CH4 analysis and carbon dioxide, respectively). However, these biases are small compared to the dampening experienced by the record due to firn smoothing. [ABSTRACT FROM AUTHOR]

We investigate for the first time the loss and alteration of past atmospheric information from air trapping mechanisms under low-accumulation conditions through continuous CH4 (and CO) measurements. Methane concentration changes were measured over the Dansgaard- Oeschger event 17 (DO-17, ∼ 60000yrBP) in the Antarctic Vostok 4G-2 ice core. Measurements were performed using continuous-flow analysis combined with laser spectroscopy. The results highlight many anomalous layers at the centimeter scale that are unevenly distributed along the ice core. The anomalous methane mixing ratios differ from those in the immediate surrounding layers by up to 50ppbv. This phenomenon can be theoretically reproduced by a simple layered trapping model, creating very localized gas age scale inversions. We propose a method for cleaning the record of anomalous values that aims at minimizing the bias in the overall signal. Once the layered-trapping-induced anomalies are removed from the record, DO-17 appears to be smoother than its equivalent record from the high-accumulation WAIS Divide ice core. This is expected due to the slower sinking and densification speeds of firn layers at lower accumulation. However, the degree of smoothing appears surprisingly similar between modern and DO-17 conditions at Vostok. This suggests that glacial records of trace gases from low-accumulation sites in the East Antarctic plateau can provide a better time resolution of past atmospheric composition changes than previously expected. We also developed a numerical method to extract the gas age distributions in ice layers after the removal of the anomalous layers based on comparison with a weakly smoothed record. It is particularly adapted for the conditions of the East Antarctic plateau, as it helps to characterize smoothing for a large range of very low-temperature and low-accumulation conditions. [ABSTRACT FROM AUTHOR]

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: 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]

Abstract: An ice core air content record that was recovered from the refrozen-recrystallization ice formation zone in the Dasuopu Glacier was investigated in this work, which showed that the air content in ice performed significant fluctuations both in the seasonal and long-time series. The air content was low in summer and high in winter, and fluctuated around the mean value of 5.025 cm3 per 100 g ice from AD 1571 to AD 1927. The correlation of the air content in ice with the climatic and environmental factors was discussed combining with the dating results, which showed that over about 400 yrs from AD 1570 to AD 1927 the air content in ice from the refrozen-recrystallization ice formation zone in the Dasuopu Glacier was mainly dominated by the insolation intensity rather than the temperature and other environmental factors in the Southern Tibetan Plateau. [Copyright &y& Elsevier]

Changes in temperature and carbon dioxide during glacial cycles recorded in Antarctic ice cores are tightly coupled. However, this relationship does not hold for interglacials. While climate cooled towards the end of both the last (Eemian) and present (Holocene) interglacials, CO 2 remained stable during the Eemian while rising in the Holocene. We identify and review twelve biogeochemical mechanisms of terrestrial (vegetation dynamics and CO 2 fertilization, land use, wildfire, accumulation of peat, changes in permafrost carbon, subaerial volcanic outgassing) and marine origin (changes in sea surface temperature, carbonate compensation to deglaciation and terrestrial biosphere regrowth, shallow-water carbonate sedimentation, changes in the soft tissue pump, and methane hydrates), which potentially may have contributed to the CO 2 dynamics during interglacials but which remain not well quantified. We use three Earth System Models (ESMs) of intermediate complexity to compare effects of selected mechanisms on the interglacial CO 2 and δ 13 CO 2 changes, focusing on those with substantial potential impacts: namely carbonate sedimentation in shallow waters, peat growth, and (in the case of the Holocene) human land use. A set of specified carbon cycle forcings could qualitatively explain atmospheric CO 2 dynamics from 8 ka BP to the pre-industrial. However, when applied to Eemian boundary conditions from 126 to 115 ka BP, the same set of forcings led to disagreement with the observed direction of CO 2 changes after 122 ka BP. This failure to simulate late-Eemian CO 2 dynamics could be a result of the imposed forcings such as prescribed CaCO 3 accumulation and/or an incorrect response of simulated terrestrial carbon to the surface cooling at the end of the interglacial. These experiments also reveal that key natural processes of interglacial CO 2 dynamics – shallow water CaCO 3 accumulation, peat and permafrost carbon dynamics - are not well represented in the current ESMs. Global-scale modeling of these long-term carbon cycle components started only in the last decade, and uncertainty in parameterization of these mechanisms is a main limitation in the successful modeling of interglacial CO 2 dynamics. [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]

Abstract: Typical rapid climate events punctuating the last glacial period in Greenland, Europe and Antarctica are compared to two rapid events occurring under warmer conditions: (i) Dansgaard–Oeschger event 25, the first abrupt warming occurring during last glacial inception; (ii) 8.2 ka BP event, the only rapid cooling recorded during the Holocene in Greenland ice cores and in Ammersee, Germany. The rate of warming during previous warmer interglacial periods is estimated from polar ice cores to 1.5 °C per millennium, without abrupt changes. Climate change expected for the 21st century should however be at least 10 times faster. To cite this article: V. Masson-Delmotte et al., C. R. Geoscience 337 (2005). [Copyright &y& Elsevier]