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Individual high-Alpine ice cores have been proven to contain a well-preserved history of past anthropogenic air pollution in western Europe. The question of how representative one ice core is with respect to the reconstruction of atmospheric composition in the source region has not been addressed so far. Here, we present the first study systematically comparing longer-term ice-core records (1750–2015 CE) of various anthropogenic compounds, such as major inorganic aerosol constituents (NH4+, NO3-, SO42-), black carbon (BC), and trace species (Cd, F−, Pb). Depending on the data availability for the different air pollutants, up to five ice cores from four high-Alpine sites located in the European Alps analysed by different laboratories were considered. Whereas absolute concentration levels can partly differ depending on the prevailing seasonal distribution of accumulated precipitation, all seven investigated anthropogenic compounds are in excellent agreement between the various sites for their respective, species-dependent longer-term concentration trends. This is related to common source regions of air pollution impacting the four sites less than 100 km away including western European countries surrounding the Alps. For individual compounds, the Alpine ice-core composites developed in this study allowed us to precisely time the onset of pollution caused by industrialization in western Europe. Extensive emissions from coal combustion and agriculture lead to an exceeding of pre-industrial (1750–1850) concentration levels already at the end of the 19th century for BC, Pb, exSO42- (non-dust, non-sea salt SO42-), and NH4+, respectively. However, Cd, F−, and NO3- concentrations started surpassing pre-industrial values only in the 20th century, predominantly due to pollution from zinc and aluminium smelters and traffic. The observed maxima of BC, Cd, F−, Pb, and exSO42- concentrations in the 20th century and a significant decline afterwards clearly reveal the efficiency of air pollution control measures such as the desulfurization of coal, the introduction of filters and scrubbers in power plants and metal smelters, and the ban of leaded gasoline improving the air quality in western Europe. In contrast, NO3- and NH4+ concentration records show levels in the beginning of the 21th century which are unprecedented in the context of the past 250 years, indicating that the introduced abatement measures to reduce these pollutants were insufficient to have a major effect at high altitudes in western Europe. Only four ice-core composite records (BC, F−, Pb, exSO42-) of the seven investigated pollutants correspond well with modelled trends, suggesting inaccuracies of the emission estimates or an incomplete representation of chemical reaction mechanisms in the models for the other pollutants. Our results demonstrate that individual ice-core records from different sites in the European Alps generally provide a spatially representative signal of anthropogenic air pollution trends in western European countries.

Three seasonally-resolved ice-core records covering the 20th century were extracted in 1994, 2004 and 2012 at a nearly identical location at the Col du Dôme (4250 m above sea level, m asl, Mont Blanc, French Alps) drill site. Here we complete and combine chemical records of major ions and radiometric measurements of 3H and 210Pb obtained on these three cores together with a 3D ice flow model of the Col du Dôme glacier, to investigate in detail the origin of the discontinuities observed in the depth-age relation of the ice cores drilled in 2004 and 2012. Taking advantage of the granitic bedrock at Col du Dôme, which makes the 210Pb ice-core records sensitive to the presence of upstream crevasses, and the fact that the depth-age disturbances are observed at depths for which absolute time markers were available, we draw an overall picture of a dynamic crevasse formation which can explain the non-disturbed depth-age relation of the ice core drilled in 1994 as well as the perturbations observed in those drilled in 2004 and 2012. Since crevasses are common at high alpine glacier sites, our study points out the mandatory need of rigorous investigations of the depth-age scale before using high alpine sites to interpret atmospheric changes.

International audience; Emission inventories indicate that thallium, a highly toxic metal, is emitted during coal burning and cement production. These estimates have been established only for the 1980s and 1990s but up to now they have not been compared to long-term observations. Here we used alpine ice cores to document thallium pollution over Europe since ∼1850. Ice-core thallium concentrations increased from 1890 to 1910, and decreased after 1965 to concentrations that were half 1890 levels. Comparison of ice-core trends, estimated past emissions, and state-of-the-art atmospheric aerosol transport modeling suggest that coal burning was responsible for thallium pollution in Europe, particularly from 1920 to 1965 because of high coal consumption at that time. The subsequent decline resulted from decreased coal consumption and reduced emissions following technological improvements. The ice-core data suggest that the rapid growth of cement production that took place in Europe after 1950 had a limited impact on thallium pollution.

This study is part of the ANR 14-CE03-0006 VIP Mont Blanc and the EU ALCOTRA AdaPT Mont Blanc project. The current paper studies the dynamics and age of the Triangle du Tacul (TDT) ice apron, a massive ice volume lying on a steep high-mountain rock wall in the French side of the Mont-Blanc massif at an altitude close to 3640 m a.s.l. Three 60 cm long ice cores were drilled to bedrock (i.e. the rock wall) in 2018 and 2019 at the TDT ice apron. Texture (microstructure and lattice-preferred orientation, LPO) analyses were performed on one core. The two remaining cores were used for radiocarbon dating of the particulate organic carbon fraction (three samples in total). Microstructure and LPO do not substantially vary with along the axis of the ice core. Throughout the core, irregularly shaped grains, associated with strain-induced grain boundary migration and strong single maximum LPO, were observed. Measurements indicate that at the TDT ice deforms under a low strain-rate simple shear regime, with a shear plane parallel to the surface slope of the ice apron. Dynamic recrystallization stands out as the major mechanism for grain growth. Micro-radiocarbon dating indicates that the TDT ice becomes older with depth perpendicular to the ice surface. We observed ice ages older than 600 year BP and at the base of the lowest 30 cm older than 3000 years. Publisher PDF

With the aim to reconstruct the history of atmospheric nitrogen pollution in south-eastern Europe, the ice core records of ammonium and nitrate covering the years 1774-2009 were extracted from a 182 m long ice core drilled in 2009 at Mount Elbrus in the Caucasus, Russia.The Elbrus ammonium ice-core record indicates a 4-fold increase from pre 1780 to 1990-2010. In summer, when both the vertical atmospheric mixing and anthropogenic ammonia emissions dominated by agriculture sector are strengthened, a moderate an increase of ammonium already took place from 1774 and 1880. The summer ammonium increase accelerated a first time at the beginning of the 20th century, and a second time after 1950, levels reaching a plateau between 1980 and 2010. This ice-core trend is compared to estimated past anthropogenic NH3 emissions in Europe by using state-of-the-art atmospheric transport (FLEXPART model driven with 0.5°x0.5° ERA-5 reanalysis data) simulations of submicron aerosol. It is shown that the ammonium Elbrus ice core trend is in excellent agreement with estimates of past NH3 emissions from south-eastern Europe (South european Russia, Turkey, southern Ukraine). The ammonium level of ice deposited prior to agricultural activities is found to represent ~11-15% of the 1980-2010 level. This value is in the lower range of estimates at the global scale of the contribution of natural ammonia emission to total (natural plus anthropic) ammonia emissions.A potentially existing trend of nitrate in the Elbrus ice core remained insignificant prior to ~1945. The well-marked 3-fold increase seen in the Elbrus ice core between 1950 and 1980 followed by a stabilization of levels between 1980 and 2010 is consistent with estimated past emissions of NOx from south-eastern Europe. In agreement with the partitioning at the global scale of natural and anthropogenic emissions of NOx, nitrate levels in Elbrus ice deposited prior to 1940 represent 26% of those deposited at the end of the 20th century.Study supported by the Megagrant project (agreement № 075-15-2021-599, 8.06.2021)

Since the 1950s, observations of radiocarbon (14C) in tropospheric carbon dioxide (CO2) have been conducted in both hemispheres, documenting the so-called nuclear “bomb spike” and its transfer into the oceans and the terrestrial biosphere, the two compartments permanently exchanging carbon with the atmosphere. Results from the Heidelberg global network of Δ14C-CO2 observations are revisited here with respect to the insights and quantitative constraints they provided on these carbon exchange fluxes. The recent development of global and hemispheric trends of Δ14C-CO2 are further discussed in regard to their suitability to continue providing constraints for 14C-free fossil CO2 emission changes on the global and regional scale.

International audience

17O-excess (Δ17O = δ17O − 0.52 × δ18O) of sulfate trapped in Antarctic ice cores has been proposed as a potential tool for assessing past oxidant chemistry, while insufficient understanding of atmospheric sulfate formation around Antarctica hampers its interpretation. To probe influences of regional specific chemistry, we compared year-round observations of Δ17O of non-sea-salt sulfate in aerosols (Δ17O(SO42−)nss) at Dome C and Dumont d’Urville, inland and coastal sites in East Antarctica, throughout the year 2011. Although Δ17O(SO42–)nss at both sites showed consistent seasonality with summer minima (~1.0 ‰) and winter maxima (~2.5 ‰) owing to sunlight-driven changes in the relative importance of O3-oxidation to OH- and H2O2-oxidation, significant inter-site differences were observed in austral spring–summer and autumn. The co-occurrence of higher Δ17O(SO42–)nss at inland (2.0 ± 0.1 ‰) than the coastal site (1.2 ± 0.1 ‰) and chemical destruction of methanesulfonate (MS–) in aerosols at inland during spring–summer (October to December), combined with the first estimated Δ17O(MS–) of ~16 ‰, implies that MS– destruction produces sulfate with high Δ17O(SO42–)nss of ~12 ‰. If contributing to the known post-depositional decrease of MS– in snow, this process should also cause a significant post-depositional increase in Δ17O(SO42–)nss over 1 ‰, that can reconcile the discrepancy between Δ17O(SO42–)nss in the atmosphere and ice.

Pollutants emitted by industrial processes are deposited across the landscape. Ice core records from mid-latitude glaciers located close to emission sources document the history of local-to-regional pollution since preindustrial times. Such records underpin attribution of pollutants to specific emission sources critical to developing abatement policies. Previous ice core studies from the Alps document the overall magnitude and timing of pollution related to nitrogen and sulfur-derived species, as well as a few metals including lead. Here, we used subannually resolved measurements of vanadium (V) and molybdenum (Mo) in two ice cores from Col du Dome (French Alps), as well as atmospheric transport and deposition modeling, to investigate sources of pollution in the free European troposphere. The noncrustal V and Mo (ncV, ncMo) components were calculated by subtracting the crustal component from the total concentration. These ice core results showed a 32-fold increase in ncV and a 69-fold increase in ncMo from the preindustrial era (pre-1860) to the industrial concentration peaks. Anthropogenic V and Mo emissions in Europe were estimated using emission factors from oil and coal consumption and atmospheric transport and deposition modeling. When comparing ice core data to estimated anthropogenic V and Mo emissions in Europe, V was found to be sourced primarily from oil combustion emissions. Conversely, coal and oil combustion estimated emissions did not agree with the measured ice core Mo concentrations, suggesting that other anthropogenic Mo sources dominated coal-burning emissions, particularly after the 1950s. Noncoal-burning sources of Mo may include metallurgy although emission factors are poorly known.

International audience; Estimates of past emission inventories suggest that toxic heavy metal pollution in Europe was highest in the mid‐1970s for lead and in the mid‐1960s for cadmium, but these previous estimates have not been compared to observations. Here, alpine ice‐cores were used to document cadmium and lead pollution in western Europe between 1890 and 2000. The ice‐core trends show that while lead pollution largely from leaded gasoline reached a maximum in ~1975 as expected, cadmium pollution primarily from zinc smelters peaked in the early‐1980s rather than in ~1965 and was up to fourfold higher than estimated after 1975. Comparisons between ice‐core trends, estimated past emissions, and state‐of‐the‐art atmospheric aerosol transport and deposition modeling suggest that the estimated decreases in cadmium emissions after 1970 were based on overly optimistic emissions reductions from the introduction of pollution control devices and other technological improvements.

Reliable estimates of fossil fuel CO2 (ffCO2) emissions from high-emission regions or urban areas are currently in demand from a wide range of players. On the one hand, cities and municipalities themselves are interested in an independent validation of their ffCO2 emissions. On the other hand, there is an increased interest in atmospheric science to merge independent emission estimate methods over different scales [Pinty et al. 2019]. 14CO2 has become the gold standard when it comes to the experimental splitting of atmospheric CO2 concentration into its biogenic and fossil components [e.g. Levin et al. 2003; 2011 or Turnbull et al. 2009].Here we report on the identification of ffCO2 emitted from the Mannheim/Ludwigshafen metropolitan region in the upper Rhine valley, Germany. Quantification of the regional ffCO2 component requires knowledge of the composition of the background air. Thus, the emission area has been sampled by an upwind and a downwind station. We will discuss the advantages and disadvantages of using local background measurements conducted at a dedicated upwind station of the emission area and compare this realisation of background estimate to regional background estimates derived from measurements at classical remote background sites. All CO2 and 14CO2 observations have been performed as part of the European RINGO project. Furthermore, we investigate the suitability of using the total-CO2 difference between the two stations as a proxy for fossil fuel CO2 and the seasonal applicability of such a surrogate tracer. Finally, the observations of the total-CO2 surrogate tracer will be compared with the predictions from STILT forward model runs. Ref.:Levin, I., B. Kromer, M. Schmidt and H. Sartorius, 2003. A novel approach for independent budgeting of fossil fuels CO2 over Europe by 14CO2 observations. Geophys. Res. Lett. 30(23), 2194, doi. 10.1029/2003GL018477.Levin, I., S. Hammer, E. Eichelmann, F. Vogel, 2011. Verification of greenhouse gas emission reductions: The prospect of atmospheric monitoring in polluted areas. Philosophical Transactions A 369, 1906-1924, doi:10.1098/rsta.2010.0249.Pinty B., P. Ciais, D. Dee, H. Dolman, M. Dowell, R. Engelen, K. Holmlund, G. Janssens-Maenhout, Y. Meijer, P. Palmer, M. Scholze, H. Denier van der Gon, M. Heimann, O. Juvyns, A. Kentarchos and H. Zunker (2019) An Operational Anthropogenic CO₂ Emissions Monitoring & Verification Support Capacity – Needs and high level requirements for in situ measurements, doi: 10.2760/182790, European Commission Joint Research Centre, EUR 29817 ENTurnbull, J., Rayner, P., Miller, J., Naegler, T., Ciais, P., & Cozic, A. (2009). On the use of 14CO2 as a tracer for fossil fuel CO2: Quantifying uncertainties using an atmospheric transport model. Journal of Geophysical Research: Atmospheres, 114(D22).

Radiometric dating of glacier ice is an essential tool where stratigraphic dating methods cannot be applied. This study focuses on Alpine glacier ice and presents a new sample preparation system for dating of glacier ice samples via radiocarbon (14C) dating of the microscopic particulate organic carbon (POC) fraction incorporated in the ice matrix. An adaptable, low-cost inline filtration-oxidation-unit (REFILOX) has been developed, which for the first time unifies all sample preparation steps from ice filtration to CO2quantification in one closed setup. A systematic14C investigation of modern European aerosol samples revealed that a POC combustion temperature of 340°C provides the best representation of the real sample age. A very low process blank of maximally 0.3±0.1 µgC now enables14C dating of high Alpine ice samples, where POC concentrations are generally low (typically 10–50 µgC/kg), in an ice sample mass range of 300–500 g. In a first successful application, the method was used to obtain age constraints for an ice core from the cold, high Alpine firn saddle Colle Gnifetti (Switzerland). Analysis of the bottom ice core sections revealed a basal age of 4171–3923 cal yr BP but also a so far enigmatic discontinuity in the age-depth relationship.

Triple oxygen isotopic compositions (Δ17O = δ17O − 0.52 × δ18O) of atmospheric sulfate (SO42−) and nitrate (NO3−) in the atmosphere reflect the relative contribution of oxidation pathways involved in their formation processes, which potentially provides information to reveal missing reactions in atmospheric chemistry models. However, there remain many theoretical assumptions for the controlling factors of Δ17O(SO42−) and Δ17O(NO3−) values in those model estimations. To test one of those assumption that Δ17O values of ozone (O3) have a flat value and do not influence the seasonality of Δ17O(SO42−) and Δ17O(NO3−) values, we performed the first simultaneous measurement of Δ17O values of atmospheric sulfate, nitrate, and ozone collected at Dumont d'Urville (DDU) Station (66°40′ S, 140°01′ E) throughout 2011. Δ17O values of sulfate and nitrate exhibited seasonal variation characterized by minima in the austral summer and maxima in winter, within the ranges of 0.9–3.4 and 23.0–41.9 ‰, respectively. In contrast, Δ17O values of ozone showed no significant seasonal variation, with values of 26 ± 1 ‰ throughout the year. These contrasting seasonal trends suggest that seasonality in Δ17O(SO42−) and Δ17O(NO3−) values is not the result of changes in Δ17O(O3), but of the changes in oxidation chemistry. The trends with summer minima and winter maxima for Δ17O(SO42−) and Δ17O(NO3−) values are caused by sunlight-driven changes in the relative contribution of O3 oxidation to the oxidation by HOx, ROx, and H2O2. In addition to that general trend, by comparing Δ17O(SO42−) and Δ17O(NO3−) values to ozone mixing ratios, we found that Δ17O(SO42−) values observed in spring (September to November) were lower than in fall (March to May), while there was no significant spring and fall difference in Δ17O(NO3−) values. The relatively lower sensitivity of Δ17O(SO42−) values to the ozone mixing ratio in spring compared to fall is possibly explained by (i) the increased contribution of SO2 oxidations by OH and H2O2 caused by NOx emission from snowpack and/or (ii) SO2 oxidation by hypohalous acids (HOX = HOCl + HOBr) in the aqueous phase.

A 22.4 m-long shallow firn core was extracted during the 2006/2007 field season from coastal Adélie Land. Annual layer counting based on subannual analyses of δ18O and major chemical components was combined with 5 reference years associated with nuclear tests and non-retreat of summer sea ice to build the initial ice-core chronology (1946–2006), stressing uncertain counting for 8 years. We focus here on the resulting δ18O and accumulation records. With an average value of 21.8 ± 6.9 cm w.e. yr−1, local accumulation shows multi-decadal variations peaking in the 1980s, but no long-term trend. Similar results are obtained for δ18O, also characterised by a remarkably low and variable amplitude of the seasonal cycle. The ice-core records are compared with regional records of temperature, stake area accumulation measurements and variations in sea-ice extent, and outputs from two models nudged to ERA (European Reanalysis) atmospheric reanalyses: the high-resolution atmospheric general circulation model (AGCM), including stable water isotopes ECHAM5-wiso (European Centre Hamburg model), and the regional atmospheric model Modèle Atmosphérique Régional (AR). A significant linear correlation is identified between decadal variations in δ18O and regional temperature. No significant relationship appears with regional sea-ice extent. A weak and significant correlation appears with Dumont d'Urville wind speed, increasing after 1979. The model-data comparison highlights the inadequacy of ECHAM5-wiso simulations prior to 1979, possibly due to the lack of data assimilation to constrain atmospheric reanalyses. Systematic biases are identified in the ECHAM5-wiso simulation, such as an overestimation of the mean accumulation rate and its interannual variability, a strong cold bias and an underestimation of the mean δ18O value and its interannual variability. As a result, relationships between simulated δ18O and temperature are weaker than observed. Such systematic precipitation and temperature biases are not displayed by MAR, suggesting that the model resolution plays a key role along the Antarctic ice sheet coastal topography. Interannual variations in ECHAM5-wiso temperature and precipitation accurately capture signals from meteorological data and stake observations and are used to refine the initial ice-core chronology within 2 years. After this adjustment, remarkable positive (negative) δ18O anomalies are identified in the ice-core record and the ECHAM5-wiso simulation in 1986 and 2002 (1998–1999), respectively. Despite uncertainties associated with post-deposition processes and signal-to-noise issues, in one single coastal ice-core record, we conclude that the S1C1 core can correctly capture major annual anomalies in δ18O as well as multi-decadal variations. These findings highlight the importance of improving the network of coastal high-resolution ice-core records, and stress the skills and limitations of atmospheric models for accumulation and δ18O in coastal Antarctic areas. This is particularly important for the overall East Antarctic ice sheet mass balance.

Sulfate aerosol (SO42−) preserved in Antarctic ice cores is discussed in the light of interactions between marine biological activity and climate since it is mainly sourced from biogenic emissions from the surface ocean and scatters solar radiation during traveling in the atmosphere. However, there has been a paradox between the ice core record and the marine sediment record; the former shows constant non-sea-salt (nss-) SO42− flux throughout the glacial-interglacial changes, and the latter shows a decrease in biogenic productivity during glacial periods compared to interglacial periods. Here, by ensuring the homogeneity of sulfur isotopic compositions of atmospheric nss-SO42− (δ34Snss) over East Antarctica, we established the applicability of the signature as a robust tool for distinguishing marine biogenic and nonmarine biogenic SO42−. Our findings, in conjunction with existing records of nss-SO42− flux and δ34Snss in Antarctic ice cores, provide an estimate of the relative importance of marine biogenic SO42− during the last glacial period to be 48 ± 10% of nss-SO42−, slightly lower than 59 ± 11% during the interglacial periods. Thus, our results tend to reconcile the ice core and sediment records, with both suggesting the decrease in marine productivity around Southern Ocean under the cold climate.

This study reports on the glaciochemistry of a deep ice core (182 m long) drilled in 2009 at Mount Elbrus (43°21′ N, 42°26′ E; 5115 m above sea level) in the Caucasus, Russia. Radiocarbon dating of the particulate organic carbon fraction in the ice suggests a basal ice age of ~ 1670 ± 400 cal yr BP. Based on chemical stratigraphy, the upper 168.6 m of the core were dated by counting annual layers. The seasonally resolved chemical records cover the years 1774–2009 (Common Era), thus, being useful to reconstruct many aspects of atmospheric pollution in central Europe from pre-industrial times to present-day. After having examined the extent to which the arrival of large dust plumes originating from Sahara and Middle East modifies the chemical composition of the Elbrus (ELB) snow and ice layers, we focus on the sulfur pollution. The ELB sulfate levels indicate a four- and six-fold increase from 1774–1900 to 1980–1995 in winter and summer, respectively. Remaining close to 116 ± 28 ppb during the nineteen century, the summer sulfate levels started to rise at a mean rate of ~ 6 ppb per year from 1920 to 1950. The summer sulfate increase accelerated between 1950 and 1975 (11 ppb per year), levels reaching a maximum between 1980 and 1990 (730 ± 152 ppb) and subsequently decreasing to 630 ± 130 ppb at the beginning of the twenty first century. Long-term sulfate trends observed in the ELB ice cores are compared with those previously obtained in Alpine ice, the most important difference consists in a more pronounced decrease of the sulfur pollution over the three last decades in western than central Europe.

Lead and antimony measurements in basal ice from the Col du Dome glacier document heavy metal pollution in western Europe associated with emissions from mining and smelting operations during European antiquity. Radiocarbon dating of the particulate organic carbon fraction in the ice suggests that the basal ice dates to ~5,000 ± 600 cal years BP. In agreement with a precisely dated Greenland lead record, the Col du Dome record indicates two periods of significant lead pollution during the Roman period, that is, the last centuries before the Common Era to the second century of the Common Era. Atmospheric modeling and the Col du Dome record consistently show an overall magnitude of the lead perturbation 100 times larger than in the Greenland record. Antimony closely tracked lead, with antimony pollution about 2 orders of magnitude lower, consistent with European peat records.

The study of the ice (cryostructures, cryostratigraphy, types and age) that partly fills the fractures in rockwall permafrost is necessary to better understand the increasing frequency/volume of rockfalls in the high alpine rockwalls. Typically inaccessible, this ice is visible only when a rockfall occurs, exposing previously hidden ice. Over the past two years, the two largest rockfalls of the decade in the Mont Blanc massif and a smaller one allowed to start the documentation of the rockwall permafrost ice. This poster aims to present the three cases. Up to now, dating has been carried out for only one of the three cases. How to date permafrost ice? Dating ice cores from alpine glaciers has shown the wide time span covered by these, from a few decades to several thousand years. Several dating methods are available to quantify the age. Counting the annual layers, which proved to be effective, is widely used in the study of mountain glaciers but cannot be used for the internal ice of the permafrost since it does not present these annual layers. Structure of the ice in the scar of the Trident of Tacul rockfall scar shows nevertheless a series of layers. We will therefore use radionuclide dating to obtain the absolute age of the ice. So far, only one age is available for interstitial ice from permafrost-affected rockwall: the ice sampled from a felt block that is part of the deposit of the 150'000 m 3 rockfall that occurred in Feb. 2014 at Piz Kesch (Swiss Alps

Multiple year-round records of bulk and size-segregated compositions of aerosol were obtained at the coastal Dumont d'Urville (DDU) and inland Concordia sites located in East Antarctica. They document the sea-salt aerosol load and composition including, for the first time in Antarctica, the bromide depletion of sea-salt aerosol relative to sodium with respect to seawater. In parallel, measurements of bromide trapped in mist chambers and denuder tubes were done to investigate the concentrations of gaseous inorganic bromine species. These data are compared to simulations done with an off-line chemistry transport model, coupled with a full tropospheric bromine chemistry scheme and a process-based sea-salt production module that includes both sea-ice-sourced and open-ocean-sourced aerosol emissions. Observed and simulated sea-salt concentrations sometime differ by up to a factor of 2 to 3, particularly at DDU possibly due to local wind pattern. In spite of these discrepancies, both at coastal and inland Antarctica, the dominance of sea-ice-related processes with respect to open ocean emissions for the sea-salt aerosol load in winter is confirmed. For summer, observations and simulations point out sea salt as the main source of gaseous inorganic bromine species. Investigations of bromide in snow pit samples do not support the importance of snowpack bromine emissions over the Antarctic Plateau. To evaluate the overall importance of the bromine chemistry over East Antarctica, BrO simulations were also discussed with respect data derived from GOME-2 satellite observations over Antarctica.

The Ninth Symposium on Polar Science/Special session: [S] Antarctic ice-ocean interaction ～observation, reconstruction, and modeling～, Tue. 4 Dec. / Entrance Hall (1st floor) at National Institute of Polar Research

Significance Our measurements show a tripling of iodine in Alpine ice between 1950 and 1990. A 20th century increase in global iodine emissions has been previously found from model simulations, based on laboratory studies, but, up to now, long-term iodine records exist only in polar regions. These polar records are influenced by sea ice processes, which may obscure global iodine trends. Our results suggest that the increased iodine deposition over the Alps is consistent with increased oceanic iodine emissions coupled with a change in the iodine speciation, both driven by increasing anthropogenic NOx emissions. In turn, the recent increase of iodine emissions implies that iodine-related ozone loss in the troposphere is more active now than in the preindustrial period., Iodine is an important nutrient and a significant sink of tropospheric ozone, a climate-forcing gas and air pollutant. Ozone interacts with seawater iodide, leading to volatile inorganic iodine release that likely represents the largest source of atmospheric iodine. Increasing ozone concentrations since the preindustrial period imply that iodine chemistry and its associated ozone destruction is now substantially more active. However, the lack of historical observations of ozone and iodine means that such estimates rely primarily on model calculations. Here we use seasonally resolved records from an Alpine ice core to investigate 20th century changes in atmospheric iodine. After carefully considering possible postdepositional changes in the ice core record, we conclude that iodine deposition over the Alps increased by at least a factor of 3 from 1950 to the 1990s in the summer months, with smaller increases during the winter months. We reproduce these general trends using a chemical transport model and show that they are due to increased oceanic iodine emissions, coupled to a change in iodine speciation over Europe from enhanced nitrogen oxide emissions. The model underestimates the increase in iodine deposition by a factor of 2, however, which may be due to an underestimate in the 20th century ozone increase. Our results suggest that iodine’s impact on the Northern Hemisphere atmosphere accelerated over the 20th century and show a coupling between anthropogenic pollution and the availability of iodine as an essential nutrient to the terrestrial biosphere.

We discuss remote terrestrial influences on boundary layer air over the Southern Ocean and Antarctica, and the mechanisms by which they arise, using atmospheric radon observations as a proxy. Our primary motivation was to enhance the scientific community’s ability to understand and quantify the potential effects of pollution, nutrient or pollen transport from distant land masses to these remote, sparsely instrumented regions. Seasonal radon characteristics are discussed at 6 stations (Macquarie Island, King Sejong, Neumayer, Dumont d’Urville, Jang Bogo and Dome Concordia) using 1–4 years of continuous observations. Context is provided for differences observed between these sites by Southern Ocean radon transects between 45 and 67°S made by the Research Vessel Investigator. Synoptic transport of continental air within the marine boundary layer (MBL) dominated radon seasonal cycles in the mid-Southern Ocean site (Macquarie Island). MBL synoptic transport, tropospheric injection, and Antarctic outflow all contributed to the seasonal cycle at the sub-Antarctic site (King Sejong). Tropospheric subsidence and injection events delivered terrestrially influenced air to the Southern Ocean MBL in the vicinity of the circumpolar trough (or “Polar Front”). Katabatic outflow events from Antarctica were observed to modify trace gas and aerosol characteristics of the MBL 100–200 km off the coast. Radon seasonal cycles at coastal Antarctic sites were dominated by a combination of local radon sources in summer and subsidence of terrestrially influenced tropospheric air, whereas those on the Antarctic Plateau were primarily controlled by tropospheric subsidence. Separate characterization of long-term marine and katabatic flow air masses at Dumont d’Urville revealed monthly mean differences in summer of up to 5 ppbv in ozone and 0.3 ng m-3 in gaseous elemental mercury. These differences were largely attributed to chemical processes on the Antarctic Plateau. A comparison of our observations with some Antarctic radon simulations by global climate models over the past two decades indicated that: (i) some models overestimate synoptic transport to Antarctica in the MBL, (ii) the seasonality of the Antarctic ice sheet needs to be better represented in models, (iii) coastal Antarctic radon sources need to be taken into account, and (iv) the underestimation of radon in subsiding tropospheric air needs to be investigated.

A 181.8 m ice core was recovered from a borehole drilled into bedrock on the western plateau of Mt El'brus (43°20′53.9′′ N, 42°25′36.0′′ E; 5115 m a.s.l.) in the Caucasus, Russia, in 2009 (Mikhalenko et al., 2015). Here, we report on the results of the water stable isotope composition from this ice core with additional data from the shallow cores. The distinct seasonal cycle of the isotopic composition allows dating by annual layer counting. Dating has been performed for the upper 126 m of the deep core combined with 20 m from the shallow cores. The whole record covers 100 years, from 2013 back to 1914. Due to the high accumulation rate (1380 mm w.e. year−1) and limited melting, we obtained isotopic composition and accumulation rate records with seasonal resolution. These values were compared with available meteorological data from 13 weather stations in the region and also with atmosphere circulation indices, back-trajectory calculations, and Global Network of Isotopes in Precipitation (GNIP) data in order to decipher the drivers of accumulation and ice core isotopic composition in the Caucasus region. In the warm season (May–October) the isotopic composition depends on local temperatures, but the correlation is not persistent over time, while in the cold season (November–April), atmospheric circulation is the predominant driver of the ice core's isotopic composition. The snow accumulation rate correlates well with the precipitation rate in the region all year round, which made it possible to reconstruct and expand the precipitation record at the Caucasus highlands from 1914 until 1966, when reliable meteorological observations of precipitation at high elevation began.

Here we review different attempts made since the early 1990s to reconstruct past forest fire activity using chemical signals recorded in ice cores extracted from the Greenland ice sheet and at a few mid-northern latitude, high-elevation glaciers. We first examined the quality of various inorganic (ammonium, nitrate, potassium) and organic (black carbon, various organic carbon compounds including levoglucosan and numerous carboxylic acids) species proposed as fire proxies in ice, particularly in Greenland. We discuss limitations in their use with respect to the considered time period (recent versus pre-industrial times), their atmospheric lifetime, and the relative importance of other non-biomass burning sources. Different high-resolution records obtained at several Greenland drill sites and covering various timescales, including the last century and Holocene, are discussed. We explore the extent to which atmospheric transport can modulate the record of boreal fires from Canada as recorded in Greenland ice. Ammonium, organic fractions (black carbon as well as organic carbon), and organic compounds like formate and vanillic acid are found to be good proxies for tracing past boreal fires in Greenland ice. We show that use of other species – potassium, nitrate, and carboxylates (except formate) – is complicated by either post-depositional effects or existence of large non-biomass-burning sources. The quality of levoglucosan with respect to other proxies is not addressed here because of the present lack of high-resolution profiles for this species, which does not allow for a fair comparison. Several Greenland ice records of ammonium consistently indicate changing fire activity in Canada in response to past climatic conditions that occurred during the last millennium and since the last large climatic transition. Based on this critical review, we make recommendations for further study to increase reliability of the reconstructed history of forest fires occurring in a given region.

In the European Alps, ice core studies have been mainly performed in view of the recent man‐made influence on the atmospheric load of aerosol‐related species, while respective investigations on the...

Regional climate model MAR (Modèle Atmosphérique Régional) was run for the region of Dome C located on the East Antarctic plateau, during Antarctic summer 2011–2012, in order to refine our understanding of meteorological conditions during the OPALE tropospheric chemistry campaign. A very high vertical resolution is set up in the lower troposphere, with a grid spacing of roughly 2 m. Model output is compared with temperatures and winds observed near the surface and from a 45 m high tower as well as sodar and radiation data. MAR is generally in very good agreement with the observations, but sometimes underestimates cloud formation, leading to an underestimation of the simulated downward long-wave radiation. Absorbed short-wave radiation may also be slightly overestimated due to an underestimation of the snow albedo, and this influences the surface energy budget and atmospheric turbulence. Nevertheless, the model provides sufficiently reliable information about surface turbulent fluxes, vertical profiles of vertical diffusion coefficients and boundary layer height when discussing the representativeness of chemical measurements made nearby the ground surface during field campaigns conducted at Concordia station located at Dome C (3233 m above sea level).

An automatic prototype aerosol sampler has been specifically revised to gain reliable year round data sets of the chemical aerosol composition at high Alpine ice core drill sites. An unattended deployment of the new aerosol sampler at the Vallot Observatory (4361 m a.s.l., French Alps) showed that previous shortcoming such as sensitivity to lightning activities and strong passive sampling effects were successfully overcome. The latter effect was almost eliminated, leading to an improvement of the detection limits by up to a factor of 30. Detailed investigations of the blank variability and sampling characteristics revealed that the new sampler allows to quantify the aerosol species NH 4 + , SO 4 2− , K + , oxalate as well as total Cl − and total NO 3 − . In addition records of Na + , Mg 2+ and Ca 2+ can be provided though systematically underestimated. On the other hand unreliable results are derived for formate, acetate and SO 2 . Considering a bi-weekly sampling interval, detection limits range from 0.2 to 2 ng m −3 STP (except for Na + : 16 ng m −3 STP). Such a detection limit is also accessible for Na + if PTFE filters are used. The aerosol data set gained at Vallot Observatory allowed preliminary estimates of mean firn/air ratios for NH 4 + , SO 4 2− and total NO 3 − . The air/firn relationship appeared to be consistent compared to other high elevation ice core drilling sites. With the improved detection limits at still minimized energy consumption, a year round deployment of the automatic aerosol sampler appears now to be feasible even at polar glacier sites.

International audience; During the 2011/12 and 2012/13 austral summers , HCHO was investigated for the first time in ambient air, snow, and interstitial air at the Concordia site, located near Dome C on the East Antarctic Plateau, by deploying an Aerolaser AL-4021 analyzer. Snow emission fluxes were estimated from vertical gradients of mixing ratios observed at 1 cm and 1 m above the snow surface as well as in interstitial air a few centimeters below the surface and in air just above the snowpack. Typical flux values range between 1 and 2 × 1012 molecules m-2 s-1 at night and 3 and 5 × 1012 molecules m-2 s-1 at noon. Shading experiments suggest that the photochemical HCHO production in the snowpack at Concordia remains negligible compared to temperature-driven air–snow exchanges. At 1 m above the snow surface, the observed mean mixing ratio of 130 pptv and its diurnal cycle characterized by a slight decrease around noon are quite well reproduced by 1-D simulations that include snow emissions and gas-phase methane oxidation chemistry. Simulations indicate that the gas-phase production from CH4 oxidation largely contributes (66 %) to the observed HCHO mixing ratios. In addition, HCHO snow emissions account for ∼ 30 % at night and ∼ 10 % at noon to the observed HCHO levels.

A high-resolution sulfate record from a Col du Dome (CDD, 4250 m above sea level, French Alps) ice core was used to investigate the impact of growing SO2 emissions on the midtroposphere sulfate levels over Europe since 1925. The large annual snow accumulation rate at the CDD site permits examination of the summer and winter sulfate trends separately. Being close to 80±10 ng g−1 in preindustrial summer ice, sulfate CDD summer levels then increase at a mean rate of 6 ng g−1 per year from 1925 to 1960. From 1960 to 1980 the increase continued at a rate of 24 ng g−1 per year. Concentrations reach a maximum of 860 ng g−1 in 1980 and subsequently decrease to 600 ng g−1 in the 1990s. These summer sulfate changes closely follow the course of growing SO2 emissions from source regions located within 700–1000 km around the Alps (France, Italy, Spain, and to a lesser extent, former West Germany). In winter the CDD sulfate levels are 3 to 8 times lower than in summer because of more limited upward transport of air masses from the boundary layer at that season. Being close to 20 ng g−1 in the preindustrial ice, winter levels were regularly enhanced at a mean annual rate of 1.2 ng g−1 from 1925 to 1980. The weak winter change from the preindustrial era to 1980 (a factor of 4 instead of 10 in summer) reflects a limited contamination of the free troposphere which, in contrast to summer, occurs at a larger scale (total Europe/former USSR). Intimately connected to Europe, these long-term changes in the Alps clearly differ in time and amplitude with the ones revealed by Greenland ice cores which indicate an increase by a factor of 3 between 1880 and 1970 in relation with long-range transport of pollutants from Eurasia as well as from North America. Furthermore, because of a lower natural contribution to the total sulfate level the anthropogenic changes can be more accurately derived in the Alps than in Greenland. Using the observed relationship between present-day concentrations in air and snowpack, the CDD ice core record permits reconstruction of present and past atmospheric sulfate concentrations at 4300 m above sea level over Europe in summer and winter. These data are compared with the sulfate levels simulated by current global sulfur models at 600 hPa for which uncertainties still range within a factor of 2. Together with observations made at lower elevation in the early 1990s the atmospheric levels derived for the CDD site (∼20 and 400 ng m−3 STP in winter and summer, respectively) document the vertical sulfate distribution between the ground and 4300 m elevation over western Europe at that time. In this way, data gained at high-elevation Alpine sites are powerful in evaluating the recent role of sulfate aerosol in forcing the climate over Europe.

In order to gain year round information on the relationship between major ions in atmospheric aerosol and deposited snow at ice core drill sites, an automatic station for filter pack sampling and for monitoring of snow height changes by vertical temperature profile readings was developed. The station was deployed for two years at a high elevation ice core drill site in the Alps (Colle Gnifetti, 4450 m asl) and thoroughly tested during several unattended campaigns for its long term reliability. Both devices showed a good long-term field performance, despite harsh environmental conditions, with the exception of data logger break downs induced by strong thunderstorms. Snow height evaluations from the vertical temperature profiles and their temporal changes provided a depth resolution of less than 5 cm and agreed well with concurrent readings from an ultra-sonic distance meter. Measurement of major ions in the autonomously sampled filter packs revealed (1) enhanced field blanks for nearly all species but no important increase of the NH + 4 to SO 2- 4 ratio during storage of exposed filters, (2) a nearly complete remobilisation of NO - 3 , Cl - and Br - from the front quartz filters and (3) a sufficiently large retention of gaseous NO - 3 , Cl - and Br - species on the back up nylon filters to allow quantification of the total concentration of these ions. Except for Na + , K + and Mg 2+ the (field blank controlled) detection limits allowed to evaluate year round atmospheric concentrations although mid-winter levels have been as low as in central Greenland during summer. The pattern and summer–winter means of atmospheric concentrations were found to be consistent with year round observations performed at a lower Alpine site as well as with the chemical snow properties at Colle Gnifetti.

In order to investigate the seasonal and geographical distribution of snow concentrations anddeposition fluxes of environmentally relevant ionic species in the Alps, the international programSNOSP was initiated. In the framework of this program, intercomparisons of snow samplingtechniques and analytical methods to determine the ionic species C1-, NO 3 - ,SO 4 2- , K+, Na+, NH4 +, Mg2+, and Ca2+, as well as the pH and the specificconductivity were performed. The concentrations of these species in the snow samples collectedin the SNOSP program varied by orders of magnitude with, e.g., concentrations of NO 3 - , SO 4 2- , and NH4 + ranging from 0.2-60, 0.2-90, and 0.1-60 µeq L-1,respectively. The intercomparisons revealed a reasonable agreement of the determinations of thespecies Cl-, NO 3 - , SO 4 2- , Na+, and NH4 + in snow. Results were less satisfactory for K+, Mg2+, Ca2+,and H+, mainly due to the very low concentrations. In conclusion, recommendations areformulated for the reliable derivation of chemical inventories from snow packs.

[1] This paper summarizes the objectives and setting of the OPALE (Oxidant Production over Antarctic Land and its Export) project during summer 2010/2011 at Dumont d'Urville. The primary goal of the campaign is to characterize the oxidizing environment of the atmospheric boundary layer along the coast of East Antarctica. A summary of the relevant field chemical measurements is presented including the carbon monoxide and ammonia records that are used here to identify local influences due to station activities and penguin emissions. An overview of the basic meteorological conditions experienced by the site is presented including the results from the trajectory/dispersion model FLEXPART to highlight which types of air mass were sampled (marine boundary layer versus continental Antarctic air). The results of the FLEXPART analysis demonstrate that high ozone levels and related changes in the OH concentrations are associated with the transport of continental air to DDU. Finally, three companion papers are introduced. A first paper is dedicated to the impact of local penguin emissions on the atmospheric budget of several oxygenated volatile organic compounds. The second paper reports on HONO levels that were measured for the first time in Antarctica by using the long path absorption photometer (LOPAP) technique. Finally, in a third paper, major findings on the HOx levels are detailed, leading to the overall conclusion that the photochemistry at coastal East Antarctica is strongly driven by an efficient HOx chemistry compared to the situation at other coastal Antarctic regions.

[1] During the austral summer 2010/2011, nitrous acid (HONO) was investigated for the first time at Concordia (75°06′S, 123°33′E) and Dumont D'Urville (66°40′S, 140°01′E), two sites located in East Antarctica. Hereby, for the first time in Antarctica, HONO was measured by deploying a long path absorption photometer (LOPAP). At Concordia, HONO mixing ratios at 1 m above the snow surface ranged between 5 and 60 pptv from end of December 2010 to mid January 2011. Lowest levels were observed under cloudy conditions. Levels exhibit a diurnal cycle with a maximum in the morning (around 06:00) and in the evening (around 21:00). At Dumont d'Urville, background mixing ratios remained close to 2 pptv in February 2011. No clear diurnal cycles were detected at that site but several events of air masses export from inland Antarctica were encountered with enhanced HONO levels (10 pptv) at night. These first HONO data gained in East Antarctica are discussed in terms of sources and sinks along with synoptic weather conditions.

[1] Initiated in 1997, the year-round study of formic and acetic acids was maintained until 2011 at the coastal Antarctic site of Dumont d'Urville. The records show that formic and acetic acids are rather abundant in summer with typical mixing ratios of 200 pptv and 700 pptv, respectively. With the aim to constrain their budget, investigations of their potential marine precursors like short-chain alkenes and acetaldehyde were initiated in 2011. Acetic acid levels in December 2010 were four times higher than those observed over summers back to 1997. These unusually high levels were accompanied by unusually high levels of ammonia, and by an enrichment of oxalate in aerosols. These observations suggest that the guano decomposition in the large penguin colonies present at the site was particularly strong under weather conditions encountered in spring 2010 (important snow storms followed by sunny days with mild temperatures). Although being dependent on environmental conditions, this process greatly impacts the local atmospheric budget of acetic acid, acetaldehyde, and acetone during the entire summer season. Present at levels as high as 500 pptv, acetaldehyde may represent the major precursor of acetic acid, alkene-ozone reactions remaining insignificant sources. Far less influenced by penguin emissions, the budget of formic acid remains not fully understood even if alkene-ozone reactions contribute significantly.

The present paper summarizes the results of SNOSP, a snow sampling program carried out in the Alps in the years from 1991 to 1993 in order to study the chemical composition of the high alpine snow pack. The paper briefly describes the sampling sites and the procedures used, focussing then on the geographical, seasonal and year to year variation of the mean concentration and total deposition of eight major ions, viz., chloride, nitrate, sulfate, ammonium, sodium, potassium, magnesium and calcium. NH 4 + , NO 3 − and SO 4 = concentrations in spring snow are higher by a factor of two to three than in winter snow since the lower tropospheric convection is confined to the valleys in winter and extends beyond glacier altitudes in spring. This underlines the importance of local and regional versus long range transport of contamination to the high elevated sites. The Ca ++ deposition occurs in single events (e.g., dust input from the Sahara) with a slightly higher incidence in spring that is consistent with the annual course of atmospheric circulation patterns. Most ionic species display a west to east increase of concentration by about one third. The prevailing precipitation patterns have opposite gradients so that total ionic load of the respective snowpack has no regional preference. The seasonal contrast as expressed by ratios of spring to winter concentrations of NH 4 + , NO 3 − and SO 4 2− is stronger in the west than in the east, and the east to west contrast is greater in winter than in spring. DOI: 10.1034/j.1600-0889.49.issue1.4.x

The particulate carbon content of precipitation was investigated in samples collected at five background sites located over a west-east European transect, from the Azores, in the mid-Atlantic Ocean, to the Hungarian plain, in central Europe. Sampling was performed on an event basis and the particulate carbon (elemental carbon, EC, and water insoluble organic carbon, WIOC) content was concentrated on quartz filters for the subsequent analysis by a thermal optical method in order to separate the EC and WIOC fractions. The average EC concentrations range from low values at the Azores (2.8±4.3 μg C L−1) and at the high mountain site of Sonnblick (5.2±3.7 μg C L−1) to high values at the more inland sites of Schauinsland (28±38 μg C L−1) and K-Puszta (24±24 μg C L−1). The average WIOC concentrations range from 98±56 μg C L−1 at the coastal site of Aveiro and 113±78 μg C L−1 at the Azores to 358±194 μg C L−1 at the continental site of K-Puszta. These results are discussed in terms of factors affecting the spatial distribution of particulate carbon, such as emissions from surrounding areas and prevalent meteorological conditions. EC is found to be a minor contributor to total particulate carbon present in rain and snow samples (from 2.5% to 15%). This is particularly true at the remotes sites, where the EC contribution to total particulate carbon is

International audience; The origin of sea-salt aerosol that reaches the high Antarctic plateau and is trapped in snow and ice cores remains still unclear. In particular, the respective role of emissions from the open ocean versus those from the sea-ice surface is not yet quantified. To progress on this question, the composition of bulk and size-segregated aerosol was studied in 2006 at the Concordia station (75°S, 123°E) located on the high Antarctic plateau. A depletion of sulfate relative to sodium with respect to the seawater composition is observed on sea-salt aerosol reaching Concordia from April to September. That suggests that in winter, when the sea-salt atmospheric load reaches a maximum, emissions from the sea-ice surface significantly contribute to the sea-salt budget of inland Antarctica. Citation: Jourdain, B., S. Preunkert, O. Cerri, H. Castebrunet, R. Udisti, and M. Legrand (2008), Year-round record of size-segregated aerosol composition in central Antarctica (Concordia station): Implications for the degree of fractionation of sea-salt particles