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We investigate the lock-in zone (LIZ) of the East Greenland Ice Core Project (EastGRIP) region, northeastern Greenland, in detail. We present results from the firn air-pumping campaign of the S6 borehole, forward modeling, and a novel technique for finding the lock-in depth (LID, the top of the LIZ) based on the visual stratigraphy of the EastGRIP ice core. The findings in this work help to deepen our knowledge of how atmospheric gases are trapped in ice cores. CO2, δ15N, and CH4 data suggest that the LID lies around 58 to 61 m depth. With the pixel value intensity and bright-spot analysis based on visual stratigraphy, we can pinpoint a change in ice properties to exactly 58.3 m depth, which we define as the optical lock-in depth (OLID). This visual change in ice properties is caused by the formation of rounded and enclosed air bubbles that alter the measured refraction of the light pathways. The results for the LID and OLID agree accurately on the depth. We furthermore use the visual stratigraphy images to obtain information on the sharpness of the open- to closed-porosity transition. Combining traditional methods with the independent optical method presented here, we can now better constrain the bubble closure processes in polar firn.

While the processes controlling pore closure are broadly understood, the physical mechanisms driving the associated elemental fractionation remains ambiguous. Previous studies have shown that the pore closure process leads to a depletion in small-sized molecules (e.g. H2, O2, Ar, Ne, He) in ice core bubbles relative to larger-sized molecules like N2. This size-dependent fractionation, identified using ice core δ(O2/N2) records, exhibits a clear anti-correlation with local summer solstice insolation, making δ(O2/N2) a valuable ice core dating tool. Mechanisms controlling this relationship are attributed to the physical properties of deep firn. In this study, we compile δ(O2/N2) records from 15 polar ice cores and show a new additional link between δ(O2/N2) and local surface temperature and/or accumulation rate. Using the Crocus snowpack model, we perform sensitivity tests to identify the response of near-surface snow properties to changes in insolation intensity, accumulation rate, and air temperature. These tests support a mechanism linked to firn grain size, such that the larger the grain size for a given density, the stronger the pore closure fractionation and, hence, the lower the δ(O2/N2) values archived in the ice. Based on both snowpack model outputs and data compilation, our findings suggest that local accumulation rate and temperature should be considered when interpreting δ(O2/N2) as a local insolation proxy.

The EPICA (European Project for Ice Coring in Antarctica) Dome C (EDC) ice core drilling in East Antarctica reaches a depth of 3260 m. The reference EDC chronology, the AICC2012 (Antarctic Ice Core Chronology 2012), provides an age vs. depth relationship covering the last 800 kyr (thousands of years), with an absolute uncertainty rising up to 8000 years at the bottom of the ice core. The origins of this relatively large uncertainty are twofold: (1) the δ18Oatm, δO2/N2 and total air content (TAC) records are poorly resolved and show large gaps over the last 800 kyr, and (2) large uncertainties are associated with their orbital targets. Here, we present new highly resolved δ18Oatm, δO2/N2 and δ15N measurements for the EDC ice core covering the last five glacial–interglacial transitions; a new low-resolution TAC record over the period 440–800 ka BP (ka: 1000 years before 1950); and novel absolute 81Kr ages. We have compiled chronological and glaciological information including novel orbital age markers from new data on the EDC ice core as well as accurate firn modeling estimates in a Bayesian dating tool to construct the new AICC2023 chronology. For the first time, three orbital tools are used simultaneously. Hence, it is possible to observe that they are consistent with each other and with the other age markers over most of the last 800 kyr (70 %). This, in turn, gives us confidence in the new AICC2023 chronology. The average uncertainty in the ice chronology is reduced from 1700 to 900 years in AICC2023 over the last 800 kyr (1σ). The new timescale diverges from AICC2012 and suggests age shifts reaching 3800 years towards older ages over marine isotope stages (MISs) 5, 11 and 19. But the coherency between the new AICC2023 timescale and independent chronologies of other archives (Italian Lacustrine succession from Sulmona Basin, Dome Fuji ice core and northern Alpine speleothems) is improved by 1000 to 2000 years over these time intervals.

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 (2σ). 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.

We present novel measurements of the carbon isotope composition of CFC-11 (CCl3F), CFC-12 (CCl2F2), and CFC-113 (CF2ClCFCl2), three atmospheric trace gases that are important for both stratospheric ozone depletion and global warming. These measurements were carried out on air samples collected in the stratosphere – the main sink region for these gases – and on air extracted from deep polar firn snow. We quantify, for the first time, the apparent isotopic fractionation, ϵapp(13C), for these gases as they are destroyed in the high- and mid-latitude stratosphere: ϵapp(CFC-12, high-latitude) =(-20.2±4.4) ‰, and ϵapp(CFC-113, high-latitude) =(-9.4±4.4) ‰, ϵapp(CFC-12, mid-latitude) =(-30.3±10.7) ‰, and ϵapp(CFC-113, mid-latitude) =(-34.4±9.8) ‰. Our CFC-11 measurements were not sufficient to calculate ϵapp(CFC-11), so we instead used previously reported photolytic fractionation for CFC-11 and CFC-12 to scale our ϵapp(CFC-12), resulting in ϵapp(CFC-11, high-latitude) =(-7.8±1.7) ‰ and ϵapp(CFC-11, mid-latitude) =(-11.7±4.2) ‰. Measurements of firn air were used to construct histories of the tropospheric isotopic composition, δT(13C), for CFC-11 (1950s to 2009), CFC-12 (1950s to 2009), and CFC-113 (1970s to 2009), with δT(13C) increasing for each gas. We used ϵapp(high-latitude), which was derived from more data, and a constant isotopic composition of emissions, δE(13C), to model δT(13C, CFC-11), δT(13C, CFC-12), and δT(13C, CFC-113). For CFC-11 and CFC-12, modelled δT(13C) was consistent with measured δT(13C) for the entire period covered by the measurements, suggesting that no dramatic change in δE(13C, CFC-11) or δE(13C, CFC-12) has occurred since the 1950s. For CFC-113, our modelled δT(13C, CFC-113) did not agree with our measurements earlier than 1980. This discrepancy may be indicative of a change in δE(13C, CFC-113). However, this conclusion is based largely on a single sample and only just significant outside the 95 % confidence interval. Therefore more work is needed to independently verify this temporal trend in the global tropospheric 13C isotopic composition of CFC-113. Our modelling predicts increasing δT(13C, CFC-11), δT(13C, CFC-12), and δT(13C, CFC-113) into the future. We investigated the effect of recently reported new CFC-11 emissions on background δT(13C, CFC-11) by fixing model emissions after 2012 and comparing δT(13C, CFC-11) in this scenario to the model base case. The difference in δT(13C, CFC-11) between these scenarios was 1.4 ‰ in 2050. This difference is smaller than our model uncertainty envelope and would therefore require improved modelling and measurement precision as well as better quantified isotopic source compositions to detect.

In the 1990s, closed and open porosity volumes of firn samples were measured by J.-M. Barnola using the technique of gas pycnometry, on firn from three different polar sites. They are the basis of a parameterization of closed porosity in polar firn, first introduced in Goujon et al. (2003) and used in several firn physics models (e.g., Buizert et al., 2012). However, these data and their processing have not been published in their own right yet. In this short article, we detail how they were processed by J.-M. Barnola and how the closed porosity parameterization was obtained. We show that the original data processing only partially accounts for the presence of reopened bubbles in the samples. Since the proper correction to apply for this effect is hard to estimate, we also processed the data without including a correction for reopened bubbles. Finally, we made these pycnometry data available in order to be used by the glaciology community, notably for the study of polar ice formation and of the composition of gas records in ice cores. They are hosted on the PANGAEA database: https://doi.org/10.1594/PANGAEA.907678 (Fourteau et al., 2019a).

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 cm ice equivalent yr−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.

We study a firn and ice core drilled at the new “Lock-In” site in East Antarctica, located 136 km away from Concordia station towards Dumont d'Urville. High-resolution chemical and physical measurements were performed on the core, with a particular focus on the trapping zone of the firn where air bubbles are formed. We measured the air content in the ice, closed and open porous volumes in the firn, firn density, firn liquid conductivity, major ion concentrations, and methane concentrations in the ice. The closed and open porosity volumes of firn samples were obtained using the two independent methods of pycnometry and tomography, which yield similar results. The measured increase in the closed porosity with density is used to estimate the air content trapped in the ice with the aid of a simple gas-trapping model. Results show a discrepancy, with the model trapping too much air. Experimental errors have been considered but do not explain the discrepancy between the model and the observations. The model and data can be reconciled with the introduction of a reduced compression of the closed porosity compared to the open porosity. Yet, it is not clear if this limited compression of closed pores is the actual mechanism responsible for the low amount of air in the ice. High-resolution density measurements reveal the presence of strong layering, manifesting itself as centimeter-scale variations. Despite this heterogeneous stratification, all layers, including the ones that are especially dense or less dense compared to their surroundings, display similar pore morphology and closed porosity as a function of density. This implies that all layers close in a similar way, even though some close in advance or later compared to the bulk firn. Investigation of the chemistry data suggests that in the trapping zone, the observed stratification is partly related to the presence of chemical impurities.

Understanding the slow densification process of polar firn into ice is essential in order to constrain the age difference between the ice matrix and entrapped gases. The progressive microstructure evolution of the firn column with depth leads to pore closure and gas entrapment. Air transport models in the firn usually include a closed porosity profile based on available data. Pycnometry or melting–refreezing techniques have been used to obtain the ratio of closed to total porosity and air content in closed pores, respectively. X-ray-computed tomography is complementary to these methods, as it enables one to obtain the full pore network in 3-D. This study takes advantage of this nondestructive technique to discuss the morphological evolution of pores on four different Antarctic sites. The computation of refined geometrical parameters for the very cold polar sites Dome C and Lock In (the two Antarctic plateau sites studied here) provides new information that could be used in further studies. The comparison of these two sites shows a more tortuous pore network at Lock In than at Dome C, which should result in older gas ages in deep firn at Lock In. A comprehensive estimation of the different errors related to X-ray tomography and to the sample variability has been performed. The procedure described here may be used as a guideline for further experimental characterization of firn samples. We show that the closed-to-total porosity ratio, which is classically used for the detection of pore closure, is strongly affected by the sample size, the image reconstruction, and spatial heterogeneities. In this work, we introduce an alternative parameter, the connectivity index, which is practically independent of sample size and image acquisition conditions, and that accurately predicts the close-off depth and density. Its strength also lies in its simple computation, without any assumption of the pore status (open or close). The close-off prediction is obtained for Dome C and Lock In, without any further numerical simulations on images (e.g., by permeability or diffusivity calculations).

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, ∼ 60 000 yr BP) 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 50 ppbv. 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.

The NOx (NO and NO2) and HOx (OH and HO2) budgets of the atmosphere exert a major influence on atmospheric composition, controlling removal of primary pollutants and formation of a wide range of secondary products, including ozone, that can influence human health and climate. However, there remain large uncertainties in the changes to these budgets over recent decades. Due to their short atmospheric lifetimes, NOx and HOx are highly variable in space and time, and so the measurements of these species are of limited value for examining long-term, large-scale changes to their budgets. Here, we take an alternative approach by examining long-term atmospheric trends of alkyl nitrates, the production efficiency of which is dependent on the atmospheric [NO] ∕ [HO2] ratio. We derive long-term trends in the alkyl nitrates from measurements in firn air from the NEEM site, Greenland. Their mixing ratios increased by a factor of 3–5 between the 1970s and 1990s. This was followed by a steep decline to the sampling date of 2008. Moreover, we examine how the trends in the alkyl nitrates compare to similarly derived trends in their parent alkanes (i.e. the alkanes which, when oxidised in the presence of NOx, lead to the formation of the alkyl nitrates). The ratios of the alkyl nitrates to their parent alkanes increased from around 1970 to the late 1990s. This is consistent with large changes to the [NO] ∕ [HO2] ratio in the Northern Hemisphere atmosphere during this period. Alternatively, they could represent changes to concentrations of the hydroxyl radical, OH, or to the transport time of the air masses from source regions to the Arctic.

The transformation of snow into ice is a complex phenomenon that is difficult to model. Depending on surface temperature and accumulation rate, it may take several decades to millennia for air to be entrapped in ice. The air is thus always younger than the surrounding ice. The resulting gas–ice age difference is essential to documenting the phasing between CO2 and temperature changes, especially during deglaciations. The air trapping depth can be inferred in the past using a firn densification model, or using δ15N of air measured in ice cores. All firn densification models applied to deglaciations show a large disagreement with δ15N measurements at several sites in East Antarctica, predicting larger firn thickness during the Last Glacial Maximum, whereas δ15N suggests a reduced firn thickness compared to the Holocene. Here we present modifications of the LGGE firn densification model, which significantly reduce the model–data mismatch for the gas trapping depth evolution over the last deglaciation at the coldest sites in East Antarctica (Vostok, Dome C), while preserving the good agreement between measured and modelled modern firn density profiles. In particular, we introduce a dependency of the creep factor on temperature and impurities in the firn densification rate calculation. The temperature influence intends to reflect the dominance of different mechanisms for firn compaction at different temperatures. We show that both the new temperature parameterization and the influence of impurities contribute to the increased agreement between modelled and measured δ15N evolution during the last deglaciation at sites with low temperature and low accumulation rate, such as Dome C or Vostok. We find that a very low sensitivity of the densification rate to temperature has to be used in the coldest conditions. The inclusion of impurity effects improves the agreement between modelled and measured δ15N at cold East Antarctic sites during the last deglaciation, but deteriorates the agreement between modelled and measured δ15N evolution at Greenland and Antarctic sites with high accumulation unless threshold effects are taken into account. We thus do not provide a definite solution to the firnification at very cold Antarctic sites but propose potential pathways for future studies.

N2O is currently the third most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes over the past decades, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using new and previously published firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290 ± 1) nmol mol−1 in 1940 to (322 ± 1) nmol mol−1 in 2008, the isotopic composition of atmospheric N2O decreased by (−2.2 ± 0.2) ‰ for δ15Nav, (−1.0 ± 0.3) ‰ for δ18O, (−1.3 ± 0.6) ‰ for δ15Nα, and (−2.8 ± 0.6) ‰ for δ15Nβ over the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric box and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to fix at 123 years. The average isotopic composition over the investigated period is δ15Nav = (−7.6 ± 0.8) ‰ (vs. air-N2), δ18O = (32.2 ± 0.2) ‰ (vs. Vienna Standard Mean Ocean Water – VSMOW) for δ18O, δ15Nα = (−3.0 ± 1.9) ‰ and δ15Nβ = (−11.7 ± 2.3) ‰. δ15Nav, and δ15Nβ show some temporal variability, while for the other signatures the error bars of the reconstruction are too large to retrieve reliable temporal changes. Possible processes that may explain trends in 15N are discussed. The 15N site preference ( = δ15Nα − δ15Nβ) provides evidence of a shift in emissions from denitrification to nitrification, although the uncertainty envelopes are large.

Chlorofluorocarbons (CFCs) are ozone-depleting substances as well as strong greenhouse gases, and the control of their production and use under the Montreal Protocol has had demonstrable benefits to both mitigation of increasing surface UV radiation and climate forcing. A global ban on consumption came into force in 2010, but there is evidence of continuing emissions of certain CFCs from a range of sources. One compound has received little attention in the literature, namely CFC-114 (C2Cl2F4). Of particular interest here is the differentiation between CFC-114 (CClF2CClF2) and its asymmetric isomeric form CFC-114a (CF3CCl2F) as atmospheric long-term measurements in the peer-reviewed literature to date have been assumed to represent the sum of both isomers with a time-invariant isomeric speciation. Here we report the first long-term measurements of the two isomeric forms separately, and find that they have different origins and trends in the atmosphere. Air samples collected at Cape Grim (41° S), Australia, during atmospheric background conditions since 1978, combined with samples collected from deep polar snow (firn) enable us to obtain a near-complete record of both gases since their initial production and release in the 1940s. Both isomers were present in the unpolluted atmosphere in comparably small amounts before 1960. The mixing ratio of CFC-114 doubled from 7.9 to 14.8 parts per trillion (ppt) between the start of the Cape Grim record in 1978 and the end of our record in 2014, while over the same time CFC-114a trebled from 0.35 to 1.03 ppt. Mixing ratios of both isomers are slowly decreasing by the end of this period. This is consistent with measurements of recent aircraft-based samples showing no significant interhemispheric mixing ratio gradient. We also find that the fraction of CFC-114a mixing ratio relative to that of CFC-114 increased from 4.2 to 6.9 % over the 37-year period. This contradicts the current tacit assumption used in international climate change and ozone depletion assessments that both isomers have been largely co-emitted and that their atmospheric concentration ratio has remained approximately constant in time. Complementary observations of air collected in Taiwan indicate a persisting source of CFC-114a in South East Asia which may have been contributing to the changing balance between the two isomers. In addition we present top-down global annual emission estimates of CFC-114 and CFC-114a derived from these measurements using a two-dimensional atmospheric chemistry-transport model. In general, the emissions for both compounds grew steadily during the 1980s, followed by a substantial reduction from the late 1980s onwards, which is consistent with the reduction of emission in response to the Montreal Protocol, and broadly consistent with bottom-up estimates derived by industry. However, we find that small but significant emissions of both isomers remain in 2014. Moreover the inferred changes to the ratio of emissions of the two isomers since the 1990s also indicate that the sources of the two gases are, in part, independent.

Perfluorocarbons (PFCs) are very potent and long-lived greenhouse gases in the atmosphere, released predominantly during aluminium production and semiconductor manufacture. They have been targeted for emission controls under the United Nations Framework Convention on Climate Change. Here we present the first continuous records of the atmospheric abundance of CF4 (PFC-14), C2F6 (PFC-116) and C3F8 (PFC-218) from 1800 to 2014. The records are derived from high-precision measurements of PFCs in air extracted from polar firn or ice at six sites (DE08, DE08-2, DSSW20K, EDML, NEEM and South Pole) and air archive tanks and atmospheric air sampled from both hemispheres. We take account of the age characteristics of the firn and ice core air samples and demonstrate excellent consistency between the ice core, firn and atmospheric measurements. We present an inversion for global emissions from 1900 to 2014. We also formulate the inversion to directly infer emission factors for PFC emissions due to aluminium production prior to the 1980s. We show that 19th century atmospheric levels, before significant anthropogenic influence, were stable at 34.1 ± 0.3 ppt for CF4 and below detection limits of 0.002 and 0.01 ppt for C2F6 and C3F8, respectively. We find a significant peak in CF4 and C2F6 emissions around 1940, most likely due to the high demand for aluminium during World War II, for example for construction of aircraft, but these emissions were nevertheless much lower than in recent years. The PFC emission factors for aluminium production in the early 20th century were significantly higher than today but have decreased since then due to improvements and better control of the smelting process. Mitigation efforts have led to decreases in emissions from peaks in 1980 (CF4) or early-to-mid-2000s (C2F6 and C3F8) despite the continued increase in global aluminium production; however, these decreases in emissions appear to have recently halted. We see a temporary reduction of around 15 % in CF4 emissions in 2009, presumably associated with the impact of the global financial crisis on aluminium and semiconductor production.

The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (ϵapp) for mid- and high-latitude stratospheric samples are respectively −2.4 (0.5) and −2.3 (0.4) ‰ for CFC-11, −12.2 (1.6) and −6.8 (0.8) ‰ for CFC-12 and −3.5 (1.5) and −3.3 (1.2) ‰ for CFC-113, where the number in parentheses is the numerical value of the standard uncertainty expressed in per mil. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these projections to the long-term δ (37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (North Greenland Eemian Ice Drilling (NEEM) site) and Antarctica (Fletcher Promontory site). From 1970 to the present day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties, a constant average emission isotope delta (δ) is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope δ has been affected by changes in CFC manufacturing processes or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 mL), using a single-detector gas chromatography–mass spectrometry (GC–MS) system.

A recent coherent chronology has been built for four Antarctic ice cores and the NorthGRIP (NGRIP) Greenland ice core (Antarctic Ice Core Chronology 2012, AICC2012) using a Bayesian approach for ice core dating (Datice). When building the AICC2012 chronology, and in order to prevent any confusion with official ice core chronology, the AICC2012 chronology for NGRIP was forced to fit exactly the GICC05 chronology based on layer counting. However, such a strong tuning did not satisfy the hypothesis of independence of background parameters and observations for the NGRIP core, as required by Datice. We present here the implementation in Datice of a new type of markers that is better suited for constraints deduced from layer counting: the duration constraints. Estimating the global error on chronology due to such markers is not straightforward and implies some assumption on the correlation between individual counting errors for each interval of duration. We validate this new methodological implementation by conducting twin experiments and a posteriori diagnostics on the NGRIP ice core. Several sensitivity tests on marker sampling and correlation between counting errors were performed to provide some guidelines when using such a method for future dating experiments. Finally, using these markers for NGRIP in a five-core dating exercise with Datice leads to new chronologies that do not differ by more than 410 years from AICC2012 for Antarctic ice cores and 150 years from GICC05 for NGRIP over the last 60 000 years.

The short-chain non-methane hydrocarbons (NMHC) are mostly emitted into the atmosphere by anthropogenic processes. Recent studies have pointed out a tight linkage between the atmospheric mole fractions of the NMHC ethane and the atmospheric growth rate of methane. Consequently, atmospheric NMHC are valuable indicators for tracking changes in anthropogenic emissions, photochemical ozone production, and greenhouse gases. This study investigates the 1950–2010 Northern Hemisphere atmospheric C2–C5 NMHC ethane, propane, i-butane, n-butane, i-pentane, and n-pentane by (a) reconstructing atmospheric mole fractions of these trace gases using firn air extracted from three boreholes in 2008 and 2009 at the North Greenland Eemian Ice Drilling (NEEM) site and applying state-of-the-art models of trace gas transport in firn, and by (b) considering eight years of ambient NMHC monitoring data from five Arctic sites within the NOAA Global Monitoring Division (GMD) Cooperative Air Sampling Network. Results indicate that these NMHC increased by ~40–120% after 1950, peaked around 1980 (with the exception of ethane, which peaked approximately 10 yr earlier), and have since dramatically decreased to be now back close to 1950 levels. The earlier peak time of ethane vs. the C3–C5 NMHC suggests that different processes and emissions mitigation measures contributed to the decline in these NMHC. The 60 yr record also illustrates notable increases in the ratios of the isomeric iso-/n-butane and iso-/n-pentane ratios. Comparison of the reconstructed NMHC histories with 1950–2000 volatile organic compounds (VOC) emissions data and with other recently published ethane trend analyses from ambient air Pacific transect data showed (a) better agreement with North America and Western Europe emissions than with total Northern Hemisphere emissions data, and (b) better agreement with other Greenland firn air data NMHC history reconstructions than with the Pacific region trends. These analyses emphasize that for NMHC, having atmospheric lifetimes on the order of < 2 months, the Greenland firn air records are primarily a representation of Western Europe and North America emission histories.

An accurate and coherent chronological framework is essential for the interpretation of climatic and environmental records obtained from deep polar ice cores. Until now, one common ice core age scale had been developed based on an inverse dating method (Datice), combining glaciological modelling with absolute and stratigraphic markers between 4 ice cores covering the last 50 ka (thousands of years before present) (Lemieux-Dudon et al., 2010). In this paper, together with the companion paper of Veres et al. (2013), we present an extension of this work back to 800 ka for the NGRIP, TALDICE, EDML, Vostok and EDC ice cores using an improved version of the Datice tool. The AICC2012 (Antarctic Ice Core Chronology 2012) chronology includes numerous new gas and ice stratigraphic links as well as improved evaluation of background and associated variance scenarios. This paper concentrates on the long timescales between 120–800 ka. In this framework, new measurements of δ18Oatm over Marine Isotope Stage (MIS) 11–12 on EDC and a complete δ18Oatm record of the TALDICE ice cores permit us to derive additional orbital gas age constraints. The coherency of the different orbitally deduced ages (from δ18Oatm, δO2/N2 and air content) has been verified before implementation in AICC2012. The new chronology is now independent of other archives and shows only small differences, most of the time within the original uncertainty range calculated by Datice, when compared with the previous ice core reference age scale EDC3, the Dome F chronology, or using a comparison between speleothems and methane. For instance, the largest deviation between AICC2012 and EDC3 (5.4 ka) is obtained around MIS 12. Despite significant modifications of the chronological constraints around MIS 5, now independent of speleothem records in AICC2012, the date of Termination II is very close to the EDC3 one.

The deep polar ice cores provide reference records commonly employed in global correlation of past climate events. However, temporal divergences reaching up to several thousand years (ka) exist between ice cores over the last climatic cycle. In this context, we are hereby introducing the Antarctic Ice Core Chronology 2012 (AICC2012), a new and coherent timescale developed for four Antarctic ice cores, namely Vostok, EPICA Dome C (EDC), EPICA Dronning Maud Land (EDML) and Talos Dome (TALDICE), alongside the Greenlandic NGRIP record. The AICC2012 timescale has been constructed using the Bayesian tool Datice (Lemieux-Dudon et al., 2010) that combines glaciological inputs and data constraints, including a wide range of relative and absolute gas and ice stratigraphic markers. We focus here on the last 120 ka, whereas the companion paper by Bazin et al. (2013) focuses on the interval 120–800 ka. Compared to previous timescales, AICC2012 presents an improved timing for the last glacial inception, respecting the glaciological constraints of all analyzed records. Moreover, with the addition of numerous new stratigraphic markers and improved calculation of the lock-in depth (LID) based on δ15N data employed as the Datice background scenario, the AICC2012 presents a slightly improved timing for the bipolar sequence of events over Marine Isotope Stage 3 associated with the seesaw mechanism, with maximum differences of about 600 yr with respect to the previous Datice-derived chronology of Lemieux-Dudon et al. (2010), hereafter denoted LD2010. Our improved scenario confirms the regional differences for the millennial scale variability over the last glacial period: while the EDC isotopic record (events of triangular shape) displays peaks roughly at the same time as the NGRIP abrupt isotopic increases, the EDML isotopic record (events characterized by broader peaks or even extended periods of high isotope values) reached the isotopic maximum several centuries before. It is expected that the future contribution of both other long ice core records and other types of chronological constraints to the Datice tool will lead to further refinements in the ice core chronologies beyond the AICC2012 chronology. For the time being however, we recommend that AICC2012 be used as the preferred chronology for the Vostok, EDC, EDML and TALDICE ice core records, both over the last glacial cycle (this study), and beyond (following Bazin et al., 2013). The ages for NGRIP in AICC2012 are virtually identical to those of GICC05 for the last 60.2 ka, whereas the ages beyond are independent of those in GICC05modelext (as in the construction of AICC2012, the GICC05modelext was included only via the background scenarios and not as age markers). As such, where issues of phasing between Antarctic records included in AICC2012 and NGRIP are involved, the NGRIP ages in AICC2012 should therefore be taken to avoid introducing false offsets. However for issues involving only Greenland ice cores, there is not yet a strong basis to recommend superseding GICC05modelext as the recommended age scale for Greenland ice cores.

We present the first reconstruction of the Northern Hemisphere (NH) high latitude atmospheric carbon monoxide (CO) mole fraction from Greenland firn air. Firn air samples were collected at three deep ice core sites in Greenland (NGRIP in 2001, Summit in 2006 and NEEM in 2008). CO records from the three sites agree well with each other as well as with recent atmospheric measurements, indicating that CO is well preserved in the firn at these sites. CO atmospheric history was reconstructed back to the year 1950 from the measurements using a combination of two forward models of gas transport in firn and an inverse model. The reconstructed history suggests that Arctic CO in 1950 was 140–150 nmol mol−1, which is higher than today's values. CO mole fractions rose by 10–15 nmol mol−1 from 1950 to the 1970s and peaked in the 1970s or early 1980s, followed by a ≈ 30 nmol mol−1 decline to today's levels. We compare the CO history with the atmospheric histories of methane, light hydrocarbons, molecular hydrogen, CO stable isotopes and hydroxyl radicals (OH), as well as with published CO emission inventories and results of a historical run from a chemistry-transport model. We find that the reconstructed Greenland CO history cannot be reconciled with available emission inventories unless unrealistically large changes in OH are assumed. We argue that the available CO emission inventories strongly underestimate historical NH emissions, and fail to capture the emission decline starting in the late 1970s, which was most likely due to reduced emissions from road transportation in North America and Europe.

Methane is a strong greenhouse gas and large uncertainties exist concerning the future evolution of its atmospheric abundance. Analyzing methane atmospheric mixing and stable isotope ratios in air trapped in polar ice sheets helps in reconstructing the evolution of its sources and sinks in the past. This is important to improve predictions of atmospheric CH4 mixing ratios in the future under the influence of a changing climate. The aim of this study is to assess whether past atmospheric δ13C(CH4) variations can be reliably reconstructed from firn air measurements. Isotope reconstructions obtained with a state of the art firn model from different individual sites show unexpectedly large discrepancies and are mutually inconsistent. We show that small changes in the diffusivity profiles at individual sites lead to strong differences in the firn fractionation, which can explain a large part of these discrepancies. Using slightly modified diffusivities for some sites, and neglecting samples for which the firn fractionation signals are strongest, a combined multi-site inversion can be performed, which returns an isotope reconstruction that is consistent with firn data. However, the isotope trends are lower than what has been concluded from Southern Hemisphere (SH) archived air samples and high-accumulation ice core data. We conclude that with the current datasets and understanding of firn air transport, a high precision reconstruction of δ13C of CH4 from firn air samples is not possible, because reconstructed atmospheric trends over the last 50 yr of 0.3–1.5 ‰ are of the same magnitude as inherent uncertainties in the method, which are the firn fractionation correction (up to ~2 ‰ at individual sites), the Kr isobaric interference (up to ~0.8 ‰, system dependent), inter-laboratory calibration offsets (~0.2 ‰) and uncertainties in past CH4 levels (~0.5 ‰).

Air and water stable isotope measurements from four Greenland deep ice cores (GRIP, GISP2, NGRIP and NEEM) are investigated over a series of Dansgaard–Oeschger events (DO 8, 9 and 10), which are representative of glacial millennial scale variability. Combined with firn modeling, air isotope data allow us to quantify abrupt temperature increases for each drill site (1σ = 0.6 °C for NEEM, GRIP and GISP2, 1.5 °C for NGRIP). Our data show that the magnitude of stadial–interstadial temperature increase is up to 2 °C larger in central and North Greenland than in northwest Greenland: i.e., for DO 8, a magnitude of +8.8 °C is inferred, which is significantly smaller than the +11.1 °C inferred at GISP2. The same spatial pattern is seen for accumulation increases. This pattern is coherent with climate simulations in response to reduced sea-ice extent in the Nordic seas. The temporal water isotope (δ18O)–temperature relationship varies between 0.3 and 0.6 (±0.08) ‰ °C−1 and is systematically larger at NEEM, possibly due to limited changes in precipitation seasonality compared to GISP2, GRIP or NGRIP. The gas age−ice age difference of warming events represented in water and air isotopes can only be modeled when assuming a 26% (NGRIP) to 40% (GRIP) lower accumulation than that derived from a Dansgaard–Johnsen ice flow model.

Correct estimation of the firn lock-in depth is essential for correctly linking gas and ice chronologies in ice core studies. Here, two approaches to constrain the firn depth evolution in Antarctica are presented over the last deglaciation: outputs of a firn densification model, and measurements of δ15N of N2 in air trapped in ice core, assuming that δ15N is only affected by gravitational fractionation in the firn column. Since the firn densification process is largely governed by surface temperature and accumulation rate, we have investigated four ice cores drilled in coastal (Berkner Island, BI, and James Ross Island, JRI) and semi-coastal (TALDICE and EPICA Dronning Maud Land, EDML) Antarctic regions. Combined with available ice core air-δ15N measurements from the EPICA Dome C (EDC) site, the studied regions encompass a large range of surface accumulation rates and temperature conditions. Our δ15N profiles reveal a heterogeneous response of the firn structure to glacial–interglacial climatic changes. While firn densification simulations correctly predict TALDICE δ15N variations, they systematically fail to capture the large millennial-scale δ15N variations measured at BI and the δ15N glacial levels measured at JRI and EDML – a mismatch previously reported for central East Antarctic ice cores. New constraints of the EDML gas–ice depth offset during the Laschamp event (~41 ka) and the last deglaciation do not favour the hypothesis of a large convective zone within the firn as the explanation of the glacial firn model–δ15N data mismatch for this site. While we could not conduct an in-depth study of the influence of impurities in snow for firnification from the existing datasets, our detailed comparison between the δ15N profiles and firn model simulations under different temperature and accumulation rate scenarios suggests that the role of accumulation rate may have been underestimated in the current description of firnification models.

A series of 12 high volume air samples collected from the S2 firn core during the North Greenland Eemian Ice Drilling (NEEM) 2009 campaign have been measured for mixing ratio and stable carbon isotope composition of the chlorofluorocarbon CFC-12 (CCl2F2). While the mixing ratio measurements compare favorably to other firn air studies, the isotope results show extreme 13C depletion at the deepest measurable depth (65 m), to values lower than δ13C = −80‰ vs. VPDB (the international stable carbon isotope scale), compared to present day surface tropospheric measurements near −40‰. Firn air modeling was used to interpret these measurements. Reconstructed atmospheric time series indicate even larger depletions (to −120‰) near 1950 AD, with subsequent rapid enrichment of the atmospheric reservoir of the compound to the present day value. Mass-balance calculations show that this change is likely to have been caused by a large change in the isotopic composition of anthropogenic CFC-12 emissions, probably due to technological advances in the CFC production process over the last 80 yr, though direct evidence is lacking.

Insoluble trace gases are trapped in polar ice at the firn-ice transition, at approximately 50 to 100 m below the surface, depending primarily on the site temperature and snow accumulation. Models of trace gas transport in polar firn are used to relate firn air and ice core records of trace gases to their atmospheric history. We propose a new model based on the following contributions. First, the firn air transport model is revised in a poromechanics framework with emphasis on the non-homogeneous properties and the treatment of gravitational settling. We then derive a nonlinear least square multi-gas optimisation scheme to calculate the effective firn diffusivity (automatic diffusivity tuning). The improvements gained by the multi-gas approach are investigated (up to ten gases for a single site are included in the optimisation process). We apply the model to four Arctic (Devon Island, NEEM, North GRIP, Summit) and seven Antarctic (DE08, Berkner Island, Siple Dome, Dronning Maud Land, South Pole, Dome C, Vostok) sites and calculate their respective depth-dependent diffusivity profiles. Among these different sites, a relationship is inferred between the snow accumulation rate and an increasing thickness of the lock-in zone defined from the isotopic composition of molecular nitrogen in firn air (denoted δ15N). It is associated with a reduced diffusivity value and an increased ratio of advective to diffusive flux in deep firn, which is particularly important at high accumulation rate sites. This has implications for the understanding of δ15N of N2 records in ice cores, in relation with past variations of the snow accumulation rate. As the snow accumulation rate is clearly a primary control on the thickness of the lock-in zone, our new approach that allows for the estimation of the lock-in zone width as a function of accumulation may lead to a better constraint on the age difference between the ice and entrapped gases.

Air was sampled from the porous firn layer at the NEEM site in Northern Greenland. We use an ensemble of ten reference tracers of known atmospheric history to characterise the transport properties of the site. By analysing uncertainties in both data and the reference gas atmospheric histories, we can objectively assign weights to each of the gases used for the depth-diffusivity reconstruction. We define an objective root mean square criterion that is minimised in the model tuning procedure. Each tracer constrains the firn profile differently through its unique atmospheric history and free air diffusivity, making our multiple-tracer characterisation method a clear improvement over the commonly used single-tracer tuning. Six firn air transport models are tuned to the NEEM site; all models successfully reproduce the data within a 1σ Gaussian distribution. A comparison between two replicate boreholes drilled 64 m apart shows differences in measured mixing ratio profiles that exceed the experimental error. We find evidence that diffusivity does not vanish completely in the lock-in zone, as is commonly assumed. The ice age- gas age difference (Δage) at the firn-ice transition is calculated to be 182+3−9 yr. We further present the first intercomparison study of firn air models, where we introduce diagnostic scenarios designed to probe specific aspects of the model physics. Our results show that there are major differences in the way the models handle advective transport. Furthermore, diffusive fractionation of isotopes in the firn is poorly constrained by the models, which has consequences for attempts to reconstruct the isotopic composition of trace gases back in time using firn air and ice core records.

We report the first data set of atmospheric abundances for the following four perfluoroalkanes: n-decafluorobutane (n-C4F10), n-dodecafluoropentane (n-C5F12), n-tetradecafluorohexane (n-C6F14) and n-hexadecafluoroheptane (n-C7F16). All four compounds could be detected and quantified in air samples from remote locations in the Southern Hemisphere (at Cape Grim, Tasmania, archived samples dating back to 1978) and the upper troposphere (a passenger aircraft flying from Germany to South Africa). Further observations originate from air samples extracted from deep firn in Greenland and allow trends of atmospheric abundances in the earlier 20th century to be inferred. All four compounds were not present in the atmosphere prior to the 1960s. n-C4F10 and n-C5F12 were also measured in samples collected in the stratosphere with the data indicating that they have no significant sinks in this region. Emissions were inferred from these observations and found to be comparable with emissions from the EDGAR database for n-C6F14. However, emissions of n-C4F10, n-C5F12 and n-C7F16 were found to differ by up to five orders of magnitude between our approach and the database. Although the abundances of the four perfluorocarbons reported here are currently small (less than 0.3 parts per trillion) they have strong Global Warming Potentials several thousand times higher than carbon dioxide (on a 100-yr time horizon) and continue to increase in the atmosphere. We estimate that the sum of their cumulative emissions reached 325 million metric tonnes CO2 equivalent at the end of 2009.

We present a 60-year record of the stable isotopes of atmospheric carbon monoxide (CO) from firn air samples collected under the framework of the North Greenland Eemian Ice Drilling (NEEM) project. CO concentration, δ13C, and δ18O of CO were measured by gas chromatography/isotope ratio mass spectrometry (gc-IRMS) from trapped gases in the firn. We applied LGGE-GIPSA firn air models (Witrant et al., 2011) to correlate gas age with firn air depth and then reconstructed the trend of atmospheric CO and its stable isotopic composition at high northern latitudes since 1950. The most probable firn air model scenarios show that δ13C decreased slightly from −25.8‰ in 1950 to −26.4‰ in 2000, then decreased more significantly to −27.2‰ in 2008. δ18O decreased more regularly from 9.8‰ in 1950 to 7.1‰ in 2008. Those same scenarios show CO concentration increased gradually from 1950 and peaked in the late 1970s, followed by a gradual decrease to present day values (Petrenko et al., 2012). Results from an isotope mass balance model indicate that a slight increase, followed by a large reduction, in CO derived from fossil fuel combustion has occurred since 1950. The reduction of CO emission from fossil fuel combustion after the mid-1970s is the most plausible mechanism for the drop of CO concentration during this time. Fossil fuel CO emissions decreased as a result of the implementation of catalytic converters and the relative growth of diesel engines, in spite of the global vehicle fleet size having grown several fold over the same time period.

Long term measurements in background air (Cape Grim, Tasmania) and firn air (NEEM, Greenland) of the potent long-lived greenhouse gas SF5CF3 show that emissions declined after the late 1990s, having grown since the 1950s, and became indistinguishable from zero after 2003. The timing of this decline suggests that emissions of this gas may have been related to the production of certain fluorochemicals; production of which have been recently phased out. An earlier observation of closely correlated atmospheric abundances of SF5CF3 and SF6 are shown here to have likely been purely coincidental, as their respective trends diverged after 2002. Due to its long lifetime (ca. 900 yr), atmospheric concentrations of SF5CF3 have not declined, and it is now well mixed between hemispheres, as is also shown here from interhemispheric aircraft measurements. Total cumulative emissions of SF5CF3 amount to around 5 kT.

We report the first measurements of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), a substitute for ozone depleting compounds, in air samples originating from remote regions of the atmosphere and present evidence for its accelerating growth. Observed mixing ratios ranged from below 0.01 ppt in deep firn air to 0.59 ppt in the current northern mid-latitudinal upper troposphere. Firn air samples collected in Greenland were used to reconstruct a history of atmospheric abundance. Year-on-year increases were deduced, with acceleration in the growth rate from 0.029 ppt per year in 2000 to 0.056 ppt per year in 2007. Upper tropospheric air samples provide evidence for a continuing growth until late 2009. Furthermore we calculated a stratospheric lifetime of 370 years from measurements of air samples collected on board high altitude aircraft and balloons. Emission estimates were determined from the reconstructed atmospheric trend and suggest that current "bottom-up" estimates of global emissions for 2005 are too high by a factor of three.

The Antarctic and sub-Antarctic methanesulphonic acid (MSA) to non sea salt sulphate (nssSO4) ratio is simulated with the Laboratoire de Météorologie Dynamique Atmospheric General Circulation Model including an atmospheric sulphur chemistry module. Spatial variations of the MSA/nssSO4 ratio in different regions have been suggested to be mostly dependent on temperature or sulphur source contributions. Its past variations in ice cores have been interpreted as related to the DMS precursor source location. Our model results are compared with available field measurements in the Antarctic and sub-Antarctic regions. This suggests that the MSA/nssSO4 ratio in the extra-tropical south hemisphere is mostly dependent on the relative importance of various DMS oxidation pathways. In order to evaluate the effect of a rapid conversion of dimethyl sulphoxide (DMSO) into MSA, not implemented in the model, the MSA+DMSO to nssSO4 ratio is also discussed. Using this modified ratio, the model mostly captures the seasonal variations of MSA/nssSO4 at mid and high-southern latitudes. In addition, the model qualitatively reproduces the bell shaped meridional variations of the ratio, which is highly dependent on the adopted relative reaction rates for the DMS+OH addition and abstraction pathways, and on the assumed reaction products of the MSIA+OH reaction. MSA/nssSO4 ratio in Antarctic snow is fairly well reproduced except at the most inland sites characterized with very low snow accumulation rates. Our results also suggest that atmospheric chemistry plays an important role in the observed decrease of the ratio in snow between coastal regions and central Antarctica. The still insufficient understanding of the DMS oxidation scheme limits our ability to model the MSA/nssSO4 ratio. Specifically, reaction products of the MSIA+OH reaction should be better quantified, and the impact of a fast DMSO conversion to MSA in spring to fall over Antarctica should be evaluated. A better understanding of BrO source processes is needed in order to include DMS + BrO chemistry in global models. Completing the observations of DMS, BrO and MSA at Halley Bay with DMSO measurements would better constrain the role of BrO in DMS oxidation. Direct measurements of MSA and nssSO4 dry deposition velocities on Antarctic snow would improve our ability to model MSA and nssSO4 in ice cores.

The budgets of seven halogenated gases (CFC-11, CFC-12, CFC-113, CFC-114, CFC-115, CCl4 and SF6) are studied by comparing measurements in polar firn air from two Arctic and three Antarctic sites, and simulation results of two numerical models: a 2-D atmospheric chemistry model and a 1-D firn diffusion model. The first one is used to calculate atmospheric concentrations from emission trends based on industrial inventories; the calculated concentration trends are used by the second one to produce depth concentration profiles in the firn. The 2-D atmospheric model is validated in the boundary layer by comparison with atmospheric station measurements, and vertically for CFC-12 by comparison with balloon and FTIR measurements. Firn air measurements provide constraints on historical atmospheric concentrations over the last century. Age distributions in the firn are discussed using a Green function approach. Finally, our results are used as input to a radiative model in order to evaluate the radiative forcing of our target gases. Multi-species and multi-site firn air studies allow to better constrain atmospheric trends. The low concentrations of all studied gases at the bottom of the firn, and their consistency with our model results confirm that their natural sources are small. Our results indicate that the emissions, sinks and trends of CFC-11, CFC-12, CFC-113, CFC-115 and SF6 are well constrained, whereas it is not the case for CFC-114 and CCl4. Significant emission-dependent changes in the lifetimes of halocarbons destroyed in the stratosphere were obtained. Those result from the time needed for their transport from the surface where they are emitted to the stratosphere where they are destroyed. Efforts should be made to update and reduce the large uncertainties on CFC lifetimes.

No abstract available.

We present the first reconstruction of the Northern Hemisphere (NH) high latitude atmospheric carbon monoxide (CO) mole fraction from Greenland firn air. Firn air samples were collected at three deep ice core sites in Greenland (NGRIP in 2001, Summit in 2006 and NEEM in 2008). CO records from the three sites agree well with each other as well as with recent atmospheric measurements, indicating that CO is well preserved in the firn at these sites. CO atmospheric history was reconstructed back to the year 1950 from the measurements using a combination of two forward models of gas transport in firn and an inverse model. The reconstructed history suggests that Arctic CO in 1950 was 140-150 nmol mol-1, which is higher than today's values. CO mole fractions rose by 10-15 nmol mol-1 from 1950 to the 1970s and peaked in the 1970s or early 1980s, followed by a ≈ 30 nmol mol-1 decline to today's levels. We compare the CO history with the atmospheric histories of methane, light hydrocarbons, molecular hydrogen, CO stable isotopes and hydroxyl radicals (OH), as well as with published CO emission inventories and results of a historical run from a chemistry-transport model. We find that the reconstructed Greenland CO history cannot be reconciled with available emission inventories unless unrealistically large changes in OH are assumed. We argue that the available CO emission inventories strongly underestimate historical NH emissions, and fail to capture the emission decline starting in the late 1970s, which was most likely due to reduced emissions from road transportation in North America and Europe. © Author(s) 2013.

To celebrate the first 10 years of Nature Reviews Neuroscience, we invited the authors of the most cited article of each year to look back on the state of their field of research at the time of publication and the impact their article has had, and to discuss the questions that might be answered in the next 10 years. This selection of highly cited articles provides interesting snapshots of the progress that has been made in diverse areas of neuroscience. They show the enormous influence of neuroimaging techniques and highlight concepts that have generated substantial interest in the past decade, such as neuroimmunology, social neuroscience and the 'network approach' to brain function. These advancements will pave the way for further exciting discoveries that lie ahead.

Ice cores drilled at Vostok Station, Antarctica, and studied over the past 10 years by Russia, France, and the United States (Figure 1) are providing a wealth of information about past climate and environmental changes over more than a full glacial-interglacial cycle. The ice cores show that East Antarctica was colder and drier during glacial periods than during the Holocene and that large-scale atmospheric circulation was more vigorous during glacial times. They also support evidence from deep-sea sediment studies favoring orbital forcing of Pleistocene climate, reveal direct correlations of carbon dioxide and methane concentrations with temperature, and indicate how the accumulation of trace compounds have changed through time.