Search

Abstract Context Clinical data on transgender children and adolescents are scarce, and sample sizes often do not allow for comparisons according to sex assigned at birth. Besides, most gender identity clinics have pointed to a recent switch in favor of an increase in the number of adolescents assigned females at birth (AFAB) over assigned males at birth (AMAB). Method We collected data on sociodemographic characteristics, and psychiatric and social vulnerabilities according to sex assigned at birth for all youths who were treated at the French largest gender identity clinic. In addition, management modalities for gender transition were discussed in multidisciplinary concertation meetings. Results We collected data from 239 youths [162(68%) AFAB, 74(32%) AMAB, and 3(1%) intersex; mean age = 14.5(± 3.16) years]. The distribution of age at referral was better explained by two clusters (C1: N = 61, mean age = 11.3 years, with more AMAB; C2: N = 175, mean age = 15.9 years with more AFAB). 215(91%) youths had gender incongruence, with 32% reporting it before puberty. School drop-out, suicidality, depression, and anxiety were common and occurred significantly more often in the AFAB group. 178(74%) youths experienced social transition within the family, and 144(61%) at school [mean age = 15.13(± 2.06) years]. The social transition was more frequent in the AFAB group. Twenty-six (11%) youths received puberty blockers [mean age = 13.87(± 2.31) years], and 105(44%) received gender-affirming hormones [mean age = 16.87(± 1.4) years]. AMABs were more likely to take puberty blockers, and there was no difference in the proportion of AMAB and AFAB taking gender-affirming hormones. Surgical requests (mainly torsoplasty) were very rare. Conclusion Age at referral should be considered when exploring gender incongruence. During adolescence, we found that gender incongruence has substantial social and psychological effects, particularly on AFAB youths, possibly explaining their higher referral rates to specialized centers, as in other specialized clinics around the world.

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.

On propose un outil de simulation prédictif de la désactivation au cours du temps d'un catalyseur d'hydrodémétallisation. Il repose sur un modèle de la géométrie du catalyseur, associé à une loi de diffusion des réactifs prenant en compte l'évolution texturale du catalyseur en cours de réaction. L'évolution de la texture est due au dépôt solide d'un des produits de la réaction dans les pores catalytiques. Le dépôt catalyse également la réaction mais de manière moins efficace que le catalyseur propre. La désactivation est liée à la diminution de la surface spécifique, et au bouchage progressif des pores. La géométrie prise en compte reflète la texture originale dite en bogue de châtaigne , qui caractérise les nouveaux catalyseurs d'hydrotraitement des résidus récemment développés à l'Institut Français du Pétrole (IFP). La simulation montre que cette géométrie particulière induit une meilleure stabilité du catalyseur vis à vis des facteurs de désactivation. Le modèle envisage d'abord une cinétique simple, tenant compte uniquement de la réaction de démétallisation. Par ailleurs, il est en mesure d'introduire une réaction compétitive pour justifier les observations expérimentales en milieu contaminé par des asphaltènes, à savoir l'occurrence des concentrations maximales en dépôt solide à l'intérieur des grains de catalyseurs, et non à leur périphérie immédiate. La simulation prédit l'évolution au cours du temps des profils le long du grain, de la surface spécifique, de la fraction de vide, de la concentration en réactif dans les pores, et de la masse de métaux déposés. Elle détermine également à chaque instant le flux du réactif à la surface du grain, ainsi que le facteur de Tamm et le taux de captation en métaux. Le modèle rend compte de manière satisfaisante des principales observations expérimentales, et constitue en outre un outil qualitatif très utile pour le développement rationnel de nouveaux catalyseurs industriels. A predictive simulation method is proposed for the deactivation of a hydrodemetallization catalyst in time. It is based on a model of the geometry of the catalyst associated with a diffusion law of the reactants, with consideration being given to the textural evolution of the catalyst during the reaction. Textural evolution is due to the solid deposition of reaction products in the catalytic pores. The deposit also catalyzes the reaction, but much less effectively than the catalyst fresh. Deactivation is linked to the decrease in the specific surface area and to the progressive plugging up of the pores. The geometry taken into consideration reflects the original socalled chestnut-burrtexture characterizing new catalysts developed by Institut Français du Pétrole (IFP) for the hydrotreatment of residues. Simulation shows that this specific geometry brings about better catalyst stability in relation to deactivation factors. The model first considers a simple kinetics involving solely the demetallization reaction. Likewise, it is capable of introducing a competitive reaction to justify experimental observations in an environment contaminated by asphaltenes, i. e. the occurrence of maximum concentrations of a solid deposit inside the catalyst grains and not on their immediate periphery. The simulation predicts the evolution in time of the profiles along the grain, the specific surface area, the void fraction, the reactant concentration in the pores and the mass of metals deposited. It also determines at all times the reactant flux on the surface of the grain as well as the Tamm factor and the metal capture rate. The model gives a satisfactory account of the leading experimental observations and also provides a very useful qualitative tool for the rational development of new industrial catalysts.

Tout comme les études aréales (area studies), les études anglophones, incluant la civilisation comme un de leur domaines de spécialité, entretiennent des rapports privilégiés avec les grands courants intellectuels transnationaux comme les postcolonial studies qui s’institutionalisent dans les universités du monde anglophone à partir des années 1980. En France, les postcolonial studies suscitèrent une levée de boucliers remarquée dans le milieu universitaire au début des années 2000 témoignant d’une hostilité, étrangement semblable aux virulentes polémiques autour des études décoloniales qui égrènent les discours médiatique, politique et académique depuis la fin des années 2010. Deux questions président ici à ma réflexion : d’une part, en quoi les critiques du postcolonialisme en France – passées et présentes – permettent-elles de penser la place de l’université française dans la division internationale du travail intellectuel ? D’autre part, quel rôle les études civilisationnelles anglophones endossent-elles dans la reproduction d’un impérialisme académique envers les pays dits du Commonwealth ? L’objectif est double : (1) contribuer au projet actuel d’historicisation du positionnement épistémologique des études anglophones en étudiant leurs rapports au postcolonialisme en contexte français et (2) évaluer l’apport de la critique décoloniale aux études civilisationnelles du Commonwealth (plus particulièrement celles qui concernent le continent africain).

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.

Objective: Newborns with congenital hypogonadotropic hypogonadism (CHH) have an impaired postnatal activation of the gonadotropic axis. Substitutive therapy with recombinant gonadotropins can be proposed to mimic physiological male mini-puberty during the first months of life. The aim of this study was to co mpare the clinical and biological efficacy of two treatment modalities of gonadotropins administration during mini-puberty in CHH neonates. Design: Multicenter retrospective analytical epidemiological study comparing two treatments, pump vs injection, between 2004 and 2019. Methods: Clinical (penile size, testis size, testicular descent) and biological parameters (serum concentrations of testosterone, anti-Müllerian hormone (AMH) and Inhibin B) were compared between the two groups by multivariate analyses. Results: Thirty-five patients were included. A significantly higher incre ase in penile length and testosterone level was observed in the injection group compared to the pump group (+0.16 ± 0.02 mm vs +0.10 ± 0.02 mm per day, P = 0.002; and +0.04 ± 0.007 ng/mL vs +0.01 ± 0.008 ng/mL per day, P = 0.001). In both groups, significant increases in penile length and width, testosterone, AMH, and Inhibin B levels were observed, as well as improved testicular descent (odds ratio of not being in a scrotal position at the end of treatment = 0.97 (0.96; 0.99)). Conclusions: Early postnatal administration of recombinant gonadotropins in CHH boys is effective in stimulating penile growth, Sertoli cell proliferati on, and testicular descent, with both treatment modalities.

Objectives: To examine the changes in diagnostic practices and clinical management of patients with 5α-reductase type 2 (SRD5A2) or 17β-hydroxysteroid dehydrogenase type 3 (HSD17B3) deficiency since molecular diagnoses became available. Methods: Clinical, laboratory, and therapeutic data were retrieved from the medical records of 52 patients with a molecular diagnosis of SRD5A2 (n = 31) or HSD17B3 (n = 21) deficiency. Temporal trends regarding age at assessment and initial sex assignment over 1994–2020 were qualitatively analyzed. Age at molecular diagnosis was compared between two subgroups of patients according to their year of birth. Results: Fifty-eight percent (n = 30) patients were diagnosed during the perinatal period, 33% (n = 17) during infancy, and 9% (n = 5) during adolescence or adulthood. Over the studied period, the patients’ age at initial assessment and diagnosis frankly decreased. The median (range) age at diagnostic confirmation was 10.5 (0–53.2) years for patients born before 2007 and 0.4 (0–9.3) years for those born in 2007 or later (P = 0.029). Genetic testing identified 27 different variants for the SRD5A2 gene (30% novel, n = 8) and 18 for the HSD17B3 gene (44% novel, n = 8). Before 2002, most patients were initially assigned as females (95%, n = 19), but this proportion dropped for those born later (44%, n = 14; P < 0.001). The influence of initial genital appearance on these decisions seemingly decreased in the most recent years. Therapeutic interventions differed according to the sex of rearing. Ten percent (n = 2) patients requested female-to-male reassignment during adulthood. Conclusion: This study showed, over the past two decades, a clear trend toward earlier diagnosis and assignment of affected newborns as males.

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.

The Mineralocorticoid Receptor (MR) mediates the sodium-retaining action of aldosterone in the distal nephron, but mechanisms regulating MR expression are still poorly understood. We previously showed that RNA Binding Proteins (RBPs) regulate MR expression at the post-transcriptional level in response to variations of extracellular tonicity. Herein, we highlight a novel regulatory mechanism involving the recruitment of microRNAs (miRNAs) under hypertonicity. RT-qPCR validated miRNAs candidates identified by high throughput screening approaches and transfection of a luciferase reporter construct together with miRNAs Mimics or Inhibitors demonstrated their functional interaction with target transcripts. Overexpression strategies using Mimics or lentivirus revealed the impact on MR expression and signaling in renal KC3AC1 cells. miR-324-5p and miR-30c-2-3p expression are increased under hypertonicity in KC3AC1 cells. These miRNAs directly affect Nr3c2 (MR) transcript stability, act with Tis11b to destabilize MR transcript but also repress Elavl1 (HuR) transcript, which enhances MR expression and signaling. Overexpression of miR-324-5p and miR-30c-2-3p alter MR expression and signaling in KC3AC1 cells with blunted responses in terms of aldosterone-regulated genes expression. We also confirm that their expression is increased by hypertonicity in vivo in the kidneys of mice treated with furosemide. These findings may have major implications for the pathogenesis of renal dysfunctions, sodium retention, and mineralocorticoid resistance.

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.

Interpretation of greenhouse gas records in polar ice cores requires a good understanding of the mechanisms controlling gas trapping in polar ice, and therefore of the processes of densification and pore closure in firn (compacted snow). Current firn densification models are based on a macroscopic description of the firn and rely on empirical laws and/or idealized geometries to obtain the equations governing the densification and pore closure. Here, we propose a physically-based methodology explicitly representing the porous structure and its evolution over time. In order to handle the complex geometry and topological changes that occur during firn densification, we rely on a Level-Set representation of the interface between the ice and the pores. Two mechanisms are considered for the displacement of the interface: (i) mass surface diffusion driven by local pore curvature and (ii) ice dislocation creep. For the latter, ice is modeled as a viscous material and the flow velocities are solutions of the Stokes equations. First applications show that the model is able to densify firn and split pores. Using the model in cold and arid conditions of the Antarctic plateau, we show that gas trapping models do not have to consider the reduced compressibility of closed pores compared to open pores in the deepest part of firns. Our results also suggest that the mechanism of curvature-driven surface diffusion does not result in pore splitting, and that ice creep has to be taken into account for pores to close. Future applications of this type of model could help quantify the evolution and closure of firn porous networks for various accumulation and temperature conditions.

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.

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.

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.

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.

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 (&varepsilon;app) 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.

This study evaluates the correlation between injuries to deep gray matter nuclei, as quantitated by lesions in these nuclei on MR T2 Fast Spin Echo (T2 FSE) images, with 6-month neurological outcome after severe traumatic brain injury (TBI).Ninety-five patients (80 males, mean age = 36.7y) with severe TBI were prospectively enrolled. All patients underwent a MR scan within the 45 days after the trauma that included a T2 FSE acquisition. A 3D deformable atlas of the deep gray matter was registered to this sequence; deep gray matter lesions (DGML) were evaluated using a semi-quantitative classification scheme. The 6-month outcome was dichotomized into unfavorable (death, vegetative or minimally conscious state) or favorable (minimal or no neurologic deficit) outcome.Sixty-six percent of the patients (63/95) had both satisfactory registration of the 3D atlas on T2 FSE and available clinical follow-up. Patients without DGML had an 89% chance (P = 0.0016) of favorable outcome while those with bilateral DGML had an 80% risk of unfavorable outcome (P = 0.00008). Multivariate analysis based on DGML accurately classified patients with unfavorable neurological outcome in 90.5% of the cases.Lesions in deep gray matter nuclei may predict long-term outcome after severe TBI with high sensitivity and specificity.

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.