ALBERT

Description: 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.

Description: Multiple year-round records of bulk and size-segregated composition of aerosol were obtained at the inland site of Concordia located at Dome C in East Antarctica. In parallel, sampling of acidic gases on denuder tubes was carried out to quantify the concentrations of HCl and HNO3 present in the gas phase. These time series are used to examine aerosol present over central Antarctica in terms of chloride depletion relative to sodium with respect to freshly emitted sea-salt aerosol as well as depletion of sulfate relative to sodium with respect to the composition of seawater. A depletion of chloride relative to sodium is observed over most of the year, reaching a maximum of  ∼ 20 ng m−3 in spring when there are still large sea-salt amounts and acidic components start to recover. The role of acidic sulfur aerosol and nitric acid in replacing chloride from sea-salt particles is here discussed. HCl is found to be around twice more abundant than the amount of chloride lost by sea-salt aerosol, suggesting that either HCl is more efficiently transported to Concordia than sea-salt aerosol or re-emission from the snow pack over the Antarctic plateau represents an additional significant HCl source. The size-segregated composition of aerosol collected in winter (from 2006 to 2011) indicates a mean sulfate to sodium ratio of sea-salt aerosol present over central Antarctica of 0.16 ± 0.05, suggesting that, on average, the sea-ice and open-ocean emissions equally contribute to sea-salt aerosol load of the inland Antarctic atmosphere. The temporal variability of the sulfate depletion relative to sodium was examined at the light of air mass backward trajectories, showing an overall decreasing trend of the ratio (i.e., a stronger sulfate depletion relative to sodium) when air masses arriving at Dome C had traveled a longer time over sea ice than over open ocean. The findings are shown to be useful to discuss sea-salt ice records extracted at deep drilling sites located inland Antarctica.

Description: Multiple year-round (2006–2015) records of the bulk and size-segregated composition of aerosol were obtained at the inland site of Concordia located in East Antarctica. The well-marked maximum of non-sea-salt sulfate (nssSO4) in January (100 ± 28 ng m−3 versus 4.4 ± 2.3 ng m−3 in July) is consistent with observations made at the coast (280 ± 78 ng m−3 in January versus 16 ± 9 ng m−3 in July at Dumont d'Urville, for instance). In contrast, the well-marked maximum of MSA at the coast in January (60 ± 23 ng m−3 at Dumont d'Urville) is not observed at Concordia (5.2 ± 2.0 ng m−3 in January). Instead, the MSA level at Concordia peaks in October (5.6 ± 1.9 ng m−3) and March (14.9 ± 5.7 ng m−3). As a result, a surprisingly low MSA-to-nssSO4 ratio (RMSA) is observed at Concordia in mid-summer (0.05 ± 0.02 in January versus 0.25 ± 0.09 in March). We find that the low value of RMSA in mid-summer at Concordia is mainly driven by a drop of MSA levels that takes place in submicron aerosol (0.3 µm diameter). The drop of MSA coincides with periods of high photochemical activity as indicated by high ozone levels, strongly suggesting the occurrence of an efficient chemical destruction of MSA over the Antarctic plateau in mid-summer. The relationship between MSA and nssSO4 levels is examined separately for each season and indicates that concentration of non-biogenic sulfate over the Antarctic plateau does not exceed 1 ng m−3 in fall and winter and remains close to 5 ng m−3 in spring. This weak non-biogenic sulfate level is discussed in the light of radionuclides (210Pb, 10Be, and 7Be) also measured on bulk aerosol samples collected at Concordia. The findings highlight the complexity in using MSA in deep ice cores extracted from inland Antarctica as a proxy of past dimethyl sulfide emissions from the Southern Ocean.

Description: We measured aerosol size distributions and conducted bulk and size-segregated aerosol sampling during two summer campaigns in January 2015 and January 2016 at the continental Antarctic station Kohnen (Dronning Maud Land). Physical and chemical aerosol properties differ conspicuously during the episodic impact of a distinctive low-pressure system in 2015 (LPS15) compared to the prevailing clear sky conditions. The approximately 3-day LPS15 located in the eastern Weddell Sea was associated with the following: marine boundary layer air mass intrusion; enhanced condensation particle concentrations (1400 ± 700 cm−3 compared to 250 ± 120 cm−3 under clear sky conditions; mean ± SD); the occurrence of a new particle formation event exhibiting a continuous growth of particle diameters (Dp) from 12 to 43 nm over 44 h (growth rate 0.6 nm h−1); peaking methane sulfonate (MS−), non-sea-salt sulfate (nss–SO42-), and Na+ concentrations (190 ng m−3 MS−, 137 ng m−3 nss–SO42-, and 53 ng m−3 Na+ compared to 24 ± 15, 107 ± 20, and 4.1 ± 2.2 ng m−3, respectively, during clear sky conditions); and finally an increased MS− ∕ nss–SO42- mass ratio βMS of 0.4 up to 2.3 (0.21 ± 0.1 under clear sky conditions) comparable to typical values found at coastal Antarctic sites. Throughout the observation period a larger part of MS− could be found in super-micron aerosol compared to nss–SO42-, i.e., (10 ± 2) % by mass compared to (3.2 ± 2) %, respectively. On the whole, under clear sky conditions aged aerosol characterized by usually mono-modal size distributions around Dp= 60 nm was observed. Although our observations indicate that the sporadic impacts of coastal cyclones were associated with enhanced marine aerosol entry, aerosol deposition on-site during austral summer should be largely dominated by typical steady clear sky conditions.

Description: Ice cores are one of the most valuable paleo-archives. Records from ice cores provide information not only about the amount of dust in the atmosphere, but also about dust sources and their changes in the past. In 2009, a 182 m long ice core was recovered from the western plateau of Mt Elbrus (5115 m a.s.l.). This record was further extended after a shallow ice core was drilled in 2013. Here we analyse Ca2+ concentrations, a commonly used proxy of dust, recorded in these Elbrus ice records over the time period of 1774–2013 CE. The Ca2+ record reveals quasi-decadal variability with a generally increasing trend. Using multiple regression analysis, we found a statistically significant spatial correlation of the Elbrus Ca2+ summer concentrations with precipitation and soil moisture content in the Levant region (specifically Syria and Iraq). The Ca2+ record also correlates with drought indices in North Africa (r=0.67, p

Description: This study reports on the glaciochemistry of a deep ice core (182 m long) drilled in 2009 at Mount Elbrus in the Caucasus, Russia. Radiocarbon dating of the particulate organic carbon fraction in the ice suggests that the basal ice dates to 280±400 CE (Common Era). Based on chemical stratigraphy, the upper 168.6 m of the core was dated by counting annual layers. The seasonally resolved chemical records cover the years 1774–2009 CE, thus being useful to reconstruct many aspects of atmospheric pollution in south-eastern Europe from pre-industrial times to the present day. After having examined the extent to which the arrival of large dust plumes originating from the Sahara and Middle East modifies the chemical composition of the Elbrus (ELB) snow and ice layers, we focus on the dust-free sulfur pollution. The ELB dust-free sulfate levels indicate a 6- and 7-fold increase from 1774–1900 to 1980–1995 in winter and summer, respectively. Remaining close to 55±10 ppb during the 19th century, the annual dust-free sulfate levels started to rise at a mean rate of ∼3 ppb per year from 1920 to 1950. The annual increase accelerated between 1950 and 1975 (8 ppb per year), with levels reaching a maximum between 1980 and 1990 (376±10 ppb) and subsequently decreasing to 270±18 ppb at the beginning of the 21st century. Long-term dust-free sulfate trends observed in the ELB ice cores are compared with those previously obtained in Alpine and Altai (Siberia) ice, with the most important differences consisting in a much earlier onset and a more pronounced decrease in the sulfur pollution over the last 3 decades in western Europe than south-eastern Europe and Siberia.

Description: 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 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 during recent vs. pre-industrial times, atmospheric lifetimes, and the relative importance of other non-biomass-burning sources. Different high-resolution records from 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 and organic carbon), and specific organic compounds such as 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 a lack of high-resolution profiles for this species, preventing 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 review, we make recommendations for further study to increase reliability of the reconstructed history of forest fires occurring in a given region.

Description: 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.

Description: A 181.2 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 (Mikhalenko et al., 2015). Here, we report on the results of the water stable isotope composition from this ice core in comparison with results from shallow ice cores. There is a distinct seasonal cycle of the isotopic composition which allowed dating by annual layer counting. Dating has been performed for the upper 126 m of the deep core combined with shallow cores data. The whole record covers one century from 2013 back to 1914. Due to the high accumulation rate (1380 mm w.e. per year) and limited melting we obtained the 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-trajectories calculations and GNIP data in order to decipher the drivers of accumulation and ice core isotopic composition in the Caucasus region. In the summer season the isotopic composition depends on the local temperature, while in winter, the atmospheric circulation is the predominant driver of the ice core isotopic composition. The snow accumulation rate correlates well with the precipitation rate in the region all year round, this made it possible to reconstruct and expand the precipitation record at the Caucasus highlands from 1914 till 1966 when the reliable meteorological observations of precipitation at high elevation began.

Description: 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.