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.

Total bromine (Br) was investigated in seasonally resolved alpine ice cores covering the 20th century. Results revealed increased Br concentrations in summer (from 0.7 ng g −1 in the late 1940s to 1.6 ng g −1 in the mid 1970s), followed by a slight decrease to 1.25 ng g −1 during the last decade of the 20th century. In winter, a more moderate increase was observed from before 1950 (0.35 ng g −1 ) to the 1970–2000 period (∼0.50 ng g −1 ). Measurements of lead suggest that ∼75% of the bromine increase in summer alpine ice between 1930–1950 and 1965–1985 was from bromine‐containing aerosol (PbBrCl) emitted during the combustion of leaded gasoline. This contribution decreased to ∼27% in 2000 following the large decrease of lead additive content in gasoline used in western Europe. Summer ice bromine concentrations, not related to PbBrCl aerosol (denoted Br y *), increased by 40% from the late 1940s to the 1990–2000 decade. In winter, the contribution of leaded‐gasoline aerosol to total bromine levels was weaker than in summer, with the winter bromine trend mainly caused by enhanced Br y * levels (∼40%) after 1950. These Br y * variations in glacial ice are discussed in terms of past atmospheric reactive bromine (Br y ) changes in the European troposphere, including anthropogenic CH 3 Br emissions and transport from the stratosphere.

Year‐round records of the ionic composition of Antarctic aerosol were obtained at the inland Dome C (DC) and coastal Neumayer (NM) sites, with additional observations of black carbon (BC) at NM. Discussions focus on the origin of ammonium in Antarctica. This first Antarctic atmospheric study of several species emitted by biomass burning (BB) indicates that BC and oxalate reach a maximum in October in relation to BB activity in the southern hemisphere. Ammonium reaches a maximum 2 months later, suggesting that BB remains a minor ammonium source there. The ammonium maximum in December coincides with the occurrence of diatom blooms in the austral ocean, suggesting that oceanic ammonia emissions are the main source of ammonium in Antarctica. The ammonium to sulfur‐derived biogenic species molar ratio of 0.15 in summer suggests far lower ammonia emissions from the Antarctic oceans than midlatitude southern oceans.

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.

Continuous all year-round samplings of atmospheric aerosol and surface snow at high (daily to 4-day) resolution were carried out at Dome C since 2004-05 to 2013 and nitrate records are here presented. Basing on a larger statistical data set than previous studies, results confirm that nitrate seasonal pattern is characterized by maxima during austral summer for both aerosol and surface snow, occurring in-phase with solar UV irradiance. This temporal pattern is likely due to a combination of nitrate sources and post-depositional processes whose intensity usually enhances during the summer. Moreover, it should be noted that a case study of the synoptic conditions, which took place during a major nitrate event, showed the occurrence of a stratosphere-troposphere exchange. The sampling of both matrices at the same time with high resolution allowed the detection of a an about one-month long recurring lag of summer maxima in snow with respect to aerosol. This result can be explained by deposition and post-deposition processes occurring at the atmosphere-snow interface, such as a net uptake of gaseous nitric acid and a replenishment of the uppermost surface layers driven by a larger temperature gradient in summer. This hypothesis was preliminarily tested by a comparison with surface layers temperature data in the 2012-13 period. The analysis of the relationship between the nitrate concentration in the gas phase and total nitrate obtained at Dome C (2012-13) showed the major role of gaseous HNO3 to the total nitrate budget suggesting the need to further investigate the gas-to-particle conversion processes.

Total OH reactivity, defined as the total loss frequency of the hydroxyl radical in the atmosphere, has proved to be an excellent tool to identify the total loading of reactive species in ambient air. High levels of unknown reactivity were found in several forests worldwide and were often higher than at urban sites.Our study presents atmospheric mixing ratios of biogenic compounds and total OH reactivity measured during late spring 2014 at the forest of downy oak trees of the Observatoire de Haute Provence (OHP), France. Air masses were sampled at two heights: 2 m, i.e., inside the canopy, and 10 m, i.e., above the canopy, where the mean canopy height is 5 m.We found that the OH reactivity at the site mainly depended on the main primary biogenic species emitted by the forest, which was isoprene and to a lesser extent by its degradation products and long-lived atmospheric compounds (up to 26 % during daytime). During daytime, no significant missing OH reactivity was reported at the site, either inside or above the canopy. However, during two nights we determined a missing fraction of OH reactivity up to 50 %, possibly due to unmeasured oxidation products. We confirmed that no significant oxidation of the primary species occurred within the canopy; primary compounds emitted by the forest were fast transported to the atmosphere. Finally, the OH reactivity at this site was maximum 69 s−1, which is a high value for a forest characterized by a temperate climate. Observations in various and diverse forests in the Mediterranean region are therefore needed to better constrain the impact of reactive gases over this area.

A 182 m ice core was recovered from a borehole drilled into bedrock on the western plateau of Mt. Elbrus (43°20´53.9'' N, 42°25´36.0'' E; 5115 m a.s.l.) in the Caucasus, Russia, in 2009. This is the first ice core in the region that represents a paleoclimate record that is practically undisturbed by seasonal melting. Relatively high snow accumulation rates at the drilling site enabled the analysis of the intraseasonal variability in climate proxies. Borehole temperatures ranged from −17 °C at 10 m depth to −2.4 °C at 182 m. A detailed radio-echo sounding survey showed that the glacier thickness ranged from 45 m near the marginal zone of the plateau up to 255 m at the glacier center. The ice core has been analyzed for stable isotopes (δ18O and δD), major ions (K+, Na+, Ca2+, Mg2+, NH4+, SO42-, NO3-, Cl-, F-), succinic acid (HOOCCH2COOH), and tritium content. The mean annual net accumulation rate of 1455 mm w.e. for the last 140 years was estimated from distinct annual oscillations of δ18O, δD, succinic acid, and NH4+. Annual layer counting also helped date the ice core, agreeing with the absolute markers of the tritium 1963 bomb horizon located at the core depth of 50.7 m w.e. and the sulfate peak of the Katmai eruption (1912) at 87.7 m w.e. According to mathematical modeling results, the ice age at the maximum glacier depth is predicted to be ~ 660 years BP. The 2009 borehole is located downstream from this point, resulting in an estimated basal ice age of less than 350–400 years BP at the drilling site. The glaciological and initial chemical analyses from the Elbrus ice core help reconstruct the atmospheric history of the European region.

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.

Mixing ratios of the atmospheric nitrogen oxides NO and NO2 were measured as part of the OPALE (Oxidant Production in Antarctic Lands & Export) campaign at Dome C, East Antarctica (75.1° S, 123.3° E, 3233 m), during December 2011 to January 2012. Profiles of NOx mixing ratios of the lower 100 m of the atmosphere confirm that, in contrast to the South Pole, air chemistry at Dome C is strongly influenced by large diurnal cycles in solar irradiance and a sudden collapse of the atmospheric boundary layer in the early evening. Depth profiles of mixing ratios in firn air suggest that the upper snowpack at Dome C holds a significant reservoir of photolytically produced NO2 and is a sink of gas-phase ozone (O3). First-time observations of bromine oxide (BrO) at Dome C show that mixing ratios of BrO near the ground are low, certainly less than 5 pptv, with higher levels in the free troposphere. Assuming steady state, observed mixing ratios of BrO and RO2 radicals are too low to explain the large NO2 : NO ratios found in ambient air, possibly indicating the existence of an unknown process contributing to the atmospheric chemistry of reactive nitrogen above the Antarctic Plateau. During 2011–2012, NOx mixing ratios and flux were larger than in 2009–2010, consistent with also larger surface O3 mixing ratios resulting from increased net O3 production. Large NOx mixing ratios at Dome C arise from a combination of continuous sunlight, shallow mixing height and significant NOx emissions by surface snow (FNOx). During 23 December 2011–12 January 2012, median FNOx was twice that during the same period in 2009–2010 due to significantly larger atmospheric turbulence and a slightly stronger snowpack source. A tripling of FNOx in December 2011 was largely due to changes in snowpack source strength caused primarily by changes in NO3− concentrations in the snow skin layer, and only to a secondary order by decrease of total column O3 and associated increase in NO3− photolysis rates. A source of uncertainty in model estimates of FNOx is the quantum yield of NO3− photolysis in natural snow, which may change over time as the snow ages.

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).

Introduction Conclusions References

Stable isotope ratios of nitrate preserved in deep ice cores are expected to provide unique and valuable information regarding paleoatmospheric processes. However, due to the post-depositional loss of nitrate in snow, this information may be erased or significantly modified by physical or photochemical processes before preservation in ice. We investigated the role of solar UV photolysis in the post-depositional modification of nitrate mass and stable isotope ratios at Dome C, Antarctica, during the austral summer of 2011/2012. Two 30 cm snow pits were filled with homogenized drifted snow from the vicinity of the base. One of these pits was covered with a plexiglass plate that transmits solar UV radiation, while the other was covered with a different plexiglass plate having a low UV transmittance. Samples were then collected from each pit at a 2–5 cm depth resolution and a 10-day frequency. At the end of the season, a comparable nitrate mass loss was observed in both pits for the top-level samples (0–7 cm) attributed to mixing with the surrounding snow. After excluding samples impacted by the mixing process, we derived an average apparent nitrogen isotopic fractionation (15ϵapp) of −67.8 ± 12 ‰ for the snow nitrate exposed to solar UV using the nitrate stable isotope ratios and concentration measurements. For the control samples in which solar UV was blocked, an apparent average 15ϵapp value of −12.0 ± 1.7 ‰ was derived. This difference strongly suggests that solar UV photolysis plays a dominant role in driving the isotopic fractionation of nitrate in snow. We have estimated a purely photolytic nitrogen isotopic fractionation (15ϵphoto) of −55.8 ± 12.0 ‰ from the difference in the derived apparent isotopic fractionations of the two experimental fields, as both pits were exposed to similar physical processes except exposure to solar UV. This value is in close agreement with the 15ϵphoto value of −47.9 ± 6.8 ‰ derived in a laboratory experiment simulated for Dome C conditions (Berhanu et al., 2014). We have also observed an insensitivity of 15ϵ with depth in the snowpack under the given experimental setup. This is due to the uniform attenuation of incoming solar UV by snow, as 15ϵ is strongly dependent on the spectral distribution of the incoming light flux. Together with earlier work, the results presented here represent a strong body of evidence that solar UV photolysis is the most relevant post-depositional process modifying the stable isotope ratios of snow nitrate at low-accumulation sites, where many deep ice cores are drilled. Nevertheless, modeling the loss of nitrate in snow is still required before a robust interpretation of ice core records can be provided.

We present high-resolution measurements of carbon monoxide (CO) concentrations from a shallow ice core of the North Greenland Eemian Ice Drilling project (NEEM-2011-S1). An optical-feedback cavity-enhanced absorption spectrometer (OF-CEAS) coupled to a continuous melter system performed continuous, online analysis during a four-week measurement campaign. This analytical setup generated stable measurements of CO concentrations with an external precision of 7.8 ppbv (1σ), based on repeated analyses of equivalent ice core sections. However, this first application of this measurement technique suffered from a poorly constrained procedural blank of 48 ± 25 ppbv and poor accuracy because an absolute calibration was not possible. The NEEM-2011-S1 CO record spans 1800 yr and the long-term trends within the most recent section of this record (i.e., post 1700 AD) resemble the existing discrete CO measurements from the Eurocore ice core. However, the CO concentration is highly variable (75–1327 ppbv range) throughout the ice core with high frequency (annual scale), high amplitude spikes characterizing the record. These CO signals are too abrupt and rapid to reflect atmospheric variability and their prevalence largely prevents interpretation of the record in terms of atmospheric CO variation. The abrupt CO spikes are likely the result of in situ production occurring within the ice itself, although the unlikely possibility of CO production driven by non-photolytic, fast kinetic processes within the continuous melter system cannot be excluded. We observe that 68% of the CO spikes are observed in ice layers enriched with pyrogenic aerosols. Such aerosols, originating from boreal biomass burning emissions, contain organic compounds, which may be oxidized or photodissociated to produce CO within the ice. However, the NEEM-2011-S1 record displays an increase of ~0.05 ppbv yr−1 in baseline CO level prior to 1700 AD (129 m depth) and the concentration remains elevated, even for ice layers depleted in dissolved organic carbon (DOC). Thus, the processes driving the likely in situ production of CO within the NEEM ice may involve multiple, complex chemical pathways not all related to past fire history and require further investigation.

Abstract. Concentrations of OH radicals and the sum of peroxy radicals, RO2, were measured in the boundary layer for the first time on the East Antarctic Plateau at the Concordia Station (Dome C, 75.10° S, 123.31° E) during the austral summer 2011/2012. The median concentrations of OH and RO2 radicals were 3.1 × 106 molecule cm−3 and 9.9 × 106 molecule cm−3, respectively. These values are comparable to those observed at the South Pole, confirming that the elevated oxidative capacity of the Antarctic atmospheric boundary layer found at the South Pole is not restricted to the South Pole but common over the high Antarctic plateau. At Concordia, the concentration of radicals showed distinct diurnal profiles with the median maximum of 5.2 × 106 molecule cm−3 at 11:00 and the median minimum of 1.1 × 106 molecule cm−3 at 01:00 for OH radicals and 1.7 × 108 molecule cm−3 and 2.5 × 107 molecule cm−3 for RO2 radicals at 13:00 and 23:00, respectively (all times are local times). Concurrent measurements of O3, HONO, NO, NO2, HCHO and H2O2 demonstrated that the major primary source of OH and RO2 radicals at Dome C was the photolysis of HONO, HCHO and H2O2, with the photolysis of HONO contributing ~75% of total primary radical production. However, photochemical modelling with accounting for all these radical sources overestimates the concentrations of OH and RO2 radicals by a factor of 2 compared to field observations. Neglecting the net OH production from HONO in the photochemical modelling results in an underestimation of the concentrations of OH and RO2 radicals by a factor of 2. To explain the observations of radicals in this case an additional source of OH equivalent to about (25–35)% of measured photolysis of HONO is required. Even with a factor of 5 reduction in the concentrations of HONO, the photolysis of HONO represents the major primary radical source at Dome C. To account for a possibility of an overestimation of NO2 observed at Dome C the calculations were also performed with NO2 concentrations estimated by assuming steady-state NO2 / NO ratios. In this case the net radical production from the photolysis of HONO should be reduced by a factor of 5 or completely removed based on the photochemical budget of OH or 0-D modelling, respectively. Another major factor leading to the large concentration of OH radicals measured at Dome C was large concentrations of NO molecules and fast recycling of peroxy radicals to OH radicals.

During the austral summer 2011/2012 atmospheric nitrous acid (HONO) was investigated for the second time at the Concordia site (75°06' S, 123°33' E), located on the East Antarctic Plateau, by deploying a long-path absorption photometer (LOPAP). Hourly mixing ratios of HONO measured in December 2011/January 2012 (35 ± 5.0 pptv) were similar to those measured in December 2010/January 2011 (30.4 ± 3.5 pptv). The large value of the HONO mixing ratio at the remote Concordia site suggests a local source of HONO in addition to weak production from oxidation of NO by the OH radical. Laboratory experiments demonstrate that surface snow removed from Concordia can produce gas-phase HONO at mixing ratios half that of the NOx mixing ratio produced in the same experiment at typical temperatures encountered at Concordia in summer. Using these lab data and the emission flux of NOx from snow estimated from the vertical gradient of atmospheric concentrations measured during the campaign, a mean diurnal HONO snow emission ranging between 0.5 and 0.8 × 109 molecules cm−2 s−1 is calculated. Model calculations indicate that, in addition to around 1.2 pptv of HONO produced by the NO oxidation, these HONO snow emissions can only explain 6.5 to 10.5 pptv of HONO in the atmosphere at Concordia. To explain the difference between observed and simulated HONO mixing ratios, tests were done both in the field and at lab to explore the possibility that the presence of HNO4 had biased the measurements of HONO.

Dissolved organic carbon (DOC) and an extended array of organic compounds were investigated in an Alpine ice core covering the 1920–1988 time period. Based on this, a reconstruction was made of the long‐term trends of water‐soluble organic carbon (WSOC) aerosol in the European atmosphere. It is shown that light mono‐ and dicarboxylates, humic‐like substances, and formaldehyde account together for more than half of the DOC content of ice. This extended chemical speciation of DOC is used to estimate the DOC fraction present in ice that is related to WSOC aerosol and its change over the past. It is suggested that after World War II, the WSOC levels have been enhanced by a factor of 2 and 3 in winter and summer, respectively. In summer, the fossil fuel contribution to the enhancement is estimated to be rather small, suggesting that it arises mainly from an increase in biogenic sources of WSOC.

Seasonally resolved chemical ice core records available from the Col du Dôme glacier (4250 m elevation, French Alps), are here used to reconstruct past aerosol load and composition of the free European troposphere from before World War II to present. Available ice core records include inorganic (Na+, Ca2+, NH4+, Cl−, NO3−, and SO42−) and organic (carboxylates, HCHO, humic-like substances, dissolved organic carbon, water-insoluble organic carbon, and black carbon) compounds and fractions that permit reconstructing the key aerosol components and their changes over the past. It is shown that the atmospheric load of submicron aerosol has been increased by a factor of 3 from the 1921–1951 to 1971–1988 years, mainly as a result of a large increase of sulfate (a factor of 5), ammonium and water-soluble organic aerosol (a factor of 3). Thus, not only growing anthropogenic emissions of sulfur dioxide and ammonia have caused the enhancement of the atmospheric aerosol load but also biogenic emissions producing water-soluble organic aerosol. This unexpected change of biospheric source of organic aerosol after 1950 needs to be considered and further investigated in scenarios dealing with climate forcing by atmospheric aerosol.

Using a newly developed method dedicated to measurements of water‐soluble humic‐like substances (HULISWS) in atmospheric aerosol samples, the carbon mass quantification of HULISWS in an Alpine ice core is achieved for the first time. The method is based on the extraction of HULISWS with a weak anion‐exchanger resin and the subsequent quantification of the extracted carbon fraction with a total organic carbon (TOC) analyzer. Measurements were performed along a Col du Dôme (4250 m above sea level, French Alps) ice core covering the 1920–2004 time period. The HULISWS concentrations exhibit a well‐marked seasonal cycle with winter minima close to 7 ppbC and summer maxima ranging between 10 and 50 ppbC. Whereas the winter HULISWS concentrations remained unchanged over the twentieth century, the summer concentrations increased from 20 ppbC prior to the Second World War to 35 ppbC in the 1970–1990s. These different trends reflect the different types of HULISWS sources in winter and summer. HULISWS are mainly primarily emitted by domestic wood burning in winter and secondary in summer being produced from biogenic precursors. For unknown reason, the HULISWS signal is found to be unusual in ice samples corresponding to World War II.