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Atmospheric sea-salt and halogen cycles play important roles in atmospheric science and chemistry including cloud processes and oxidation capacity in the Antarctic troposphere. This paper presents a review and summarizes current knowledge related to sea-salt and halogen chemistry in the Antarctic. First, presented are the seasonal variations and size distribution of sea-salt aerosols (SSAs). Second, SSA origins and sea-salt fractionation on sea-ice and ice sheets on the Antarctic continent are presented and discussed. Third, we discuss SSA release from the cryosphere. Fourth, we present SSA dispersion in the Antarctic troposphere and transport into inland areas. Fifth, heterogeneous reactions on SSAs as a source of reactive halogen species and their relationship with atmospheric chemistry are shown and discussed. Finally, we attempt to propose an outlook for obtaining better knowledge related to sea-salt and halogen chemistry and their effects on the Antarctic and the Arctic.

Key Points: • First ever measurements with a high‐accuracy single‐particle soot photometer of black carbon (BC) concentrations in Arctic snowpack • Topography and BC emission flux strongly influenced latitudinal variations of mass concentrations and size distributions of BC • Measured BC mass concentrations 2–25 times lower than previously reported show the importance of revalidating climate models Black carbon (BC) deposited on snow lowers its albedo, potentially contributing to warming in the Arctic. Atmospheric distributions of BC and inorganic aerosols, which contribute directly and indirectly to radiative forcing, are also greatly influenced by depositions. To quantify these effects, accurate measurement of the spatial distributions of BC and ionic species representative of inorganic aerosols (ionic species hereafter) in snowpack in various regions of the Arctic is needed, but few such measurements are available. We measured mass concentrations of size-resolved BC (CMBC) and ionic species in snowpack by using a single-particle soot photometer and ion chromatography, respectively, over Finland, Alaska, Siberia, Greenland, and Spitsbergen during early spring in 2012–2016. Total BC mass deposited per unit area (DEPMBC) during snow accumulation periods was derived from CMBC and snow water equivalent (SWE). Our analyses showed that the spatial distributions of anthropogenic BC emission flux, total precipitable water, and topography strongly influenced latitudinal variations of CMBC, BC size distributions, SWE, and DEPMBC. The average size distributions of BC in Arctic snowpack shifted to smaller sizes with decreasing CMBC due to an increase in the removal efficiency of larger BC particles during transport from major sources. Our measurements of CMBC were lower by a factor of ~13 than previous measurements made with an Integrating Sphere/Integrating Sandwich spectrophotometer due mainly to interference from coexisting non-BC particles such as mineral dust. The SP2 data presented here will be useful for constraining climate models that estimate the effects of BC on the Arctic climate. Plain Language Summary Black carbon (BC) particles, commonly known as soot, are emitted from incomplete combustion of fossil fuels and biomass. They efficiently absorb solar radiation and thus heat the atmosphere. BC particles emitted at midlatitudes and in the Arctic are deposited onto snow in the Arctic, accelerating snowmelt in early spring by absorbing solar radiation. These processes contribute to warming in the Arctic. Calculations of this warming effect by using numerical models need to be validated by comparison with observed BC concentrations in snowpack. However, there are very few accurate records of concentrations of BC in snow because of technical difficulties in making these measurements. We developed a new laser-induced incandescence technique to measure BC concentrations in snowpack and applied it for the first time in six Arctic regions (Finland, Alaska, North and South Siberia, Greenland, and Spitsbergen). The BC concentrations we measured were highest in Finland and South Siberia, which are closer to large anthropogenic BC sources than the other regions, where our measured BC concentrations were much lower. On average, our BC concentrations were much lower than those previously measured by different techniques. Therefore, previous comparisons of modeled and observed BC concentrations need to be re-evaluated using the present data.

Temporal variability in surface mass balance (SMB) on the Greenland ice sheet is important for understanding the mass balance of the ice sheet. Additionally, knowledge of the spatial variability in SMB at ice core drilling sites helps to interpret the spatial representativeness of SMB data obtained from a single ice core. In this study, to investigate the spatiotemporal variability in recent SMB in the East Greenland Ice Core Project (EGRIP) area in the northeastern Greenland ice sheet, pit observations were made at six sites in the summers of 2016–2018. In all pits, depth profiles of water isotope ratios showed clear seasonal variations. The annual SMB differed from site to site, which is probably due to post-depositional redistribution of snow caused by wind erosion and snowdrift. However, the multiple-site averages of annual SMBs, which ranged from 134 to 157 mm w. e. yr−1 (average 146 mm w. e. yr−1) during 2009–2017, were very similar. This indicates that annual SMBs in the EGRIP area were nearly constant in this period. The seasonal SMBs in the EGRIP area tended to be larger in the summer–winter period than in the winter–summer period.

We collected snow samples from two pits with depths of 4.02 and 3.18 m at the East Greenland Ice Core Project camp (75°37′N, 35°59′W), Greenland in the summer of 2016 to estimate recent annual snow deposition and examine seasonal variation in major ion species, stable isotopes of water and microparticles (dust). Dating based on clear seasonal variation in chemical components indicated that the 4.02- and 3.18-m-deep pits included snow deposition corresponding to ten years from 2006 to 2016 and seven years from 2009 to 2016, respectively. The mean values for annual snow deposition for the 4.02-m-deep pit were 138 and 145 mm yr−1 in water equivalent (mm w.e. Yr−1) in 2006–2016 and 2009–2016, respectively. The average deposition for the 3.18-m-deep pit was 149 mm w.e. Yr−1 between 2009 and 2016. Seasonal variation in concentrations of major ion species and dust were similar to those previously reported for Greenland. The maximum Cl−/Na+ concentration ratios in the summer were much higher than the ratios at other sites in Greenland.

We examine a firn core from a dome in southeast Greenland that exhibits distinct firn densification. The ice was -20.9 °C at 20 m depth, and the core gives an average accumulation rate of 1.0 m w.e. yr-1 in water equivalent. However, the close-off density of 830 kg m-3 occurs at 83.4–86.8 m depth, which is about 20-m shallower than that obtained from two empirical models. Where the density ρ > 750 kg m-3, the densification appears faster than that from the empirical models. As a result, compared to the empirical coefficient, the actual compactive viscosity coefficient is nonlinear and decreases at ρ > 750 kg m-3, indicating that the firn with a higher density is softer than that from the empirical result. We argue here that the high accumulation rate creates a high overburden pressure in a short time. Thus, the relative softness of the firn may arise from (1) there being not enough time to form bonds between grains as strong as those in a lower accumulation-rate area, and similarly, (2) the dislo...

The deepest ice in inland Antarctica is expected to preserve the oldest ice records and to potentially contain microorganisms. However, little is known about the physicochemical conditions in the deepest part of ice sheets. This study investigates the physicochemical properties of the bottom section (3000–3035 m) of the Dome Fuji inland ice core, which is located immediately above unfrozen bedrock. The ubiquitous presence of air hydrates and the water isotope composition of ice comparable to the upper main ice core show that the bottom ice is meteoric. However, ion concentrations exhibit abnormal drops at the greatest depths (approximately below 3033 m). In the same depth range, microscopic investigations reveal that considerable relocation of air hydrates and micro-inclusions (water-soluble impurities) occurs, suggesting that the observed reduction in ion concentration results from the segregation of inclusions to ice grain boundaries and the subsequent discharge of chemicals through liquid-water veins. Principal component analysis of ion data supports the meteoric-ice hypothesis, suggesting that the bottom ice had similar original chemistry through all depths. Statistical analyses of chemical data suggest that the water-soluble impurities attached to hydrates or dust (water-insoluble), the ice-soluble chemical species (such as chlorine), and solid particles are less affected by this chemical displacement phenomenon. It is also noteworthy that, in the bottom ice, impurity chemicals, which are limiting nutrients for ice-dwelling microorganisms, are concentrated largely to ice–hydrate interfaces, where oxygen, another vital matter for aerobic microorganisms, is also enriched.

The sulfur stable isotopic values (δ34S) of sulfate aerosols can be used to assess oxidation pathways and contributions from various sources, such as marine biogenic sulfur, volcanoes, and sea salt. However, because of a lack of observations, the spatial distribution of δ34S values in Antarctic sulfate aerosols remains unclear. Here we present the first sulfur isotopic values from surface snow samples along a latitudinal transect in eastern Dronning Maud Land, East Antarctica. The δ34S values of sulfate showed remarkably uniform values, in the range of 14.8–16.9‰, and no significant decrease toward the inland part of the transect was noted. These results suggest that net isotopic fractionation during long-range transport is insignificant. Thus, the δ34S values can be used to infer source contributions. The δ34S values suggest that marine biogenic sulfur is the dominant source of sulfate aerosols, with a fractional contribution of 84 ± 16%.

Geological reconstruction of the retreat history of the East Antarctic Ice Sheet (EAIS) since the Last Glacial Maximum (LGM) is essential for understanding the response of the ice sheet to global climatic change and the mechanisms of retreat, including a possible abrupt melting event. Such information is key for constraining climatic and ice-sheet models that are used to predict future Antarctic Ice Sheet AIS melting. However, data required to make a detailed reconstruction of the history of the EAIS involving changes in its thickness and lateral extent since the LGM remain sparse. Here, we present a new detailed ice-sheet history for the southern Soya Coast, Lutzow-Holm Bay, East Antarctica, based on geomorphological observations and surface exposure ages. Our results demonstrate that the ice sheet completely covered the highest peak of Skarvsnes (400 m a.s.l.) prior to ∼9 ka and retreated eastward by at least 10 km during the Early to Mid-Holocene (ca. 9 to 5 ka). The timing of the abrupt ice-sheet thinning and retreat is consistent with the intrusion of modified Circumpolar Deep Water (mCDW) into deep submarine valleys in Lutzow-Holm Bay, as inferred from fossil foraminifera records of marine sediment cores. Thus, we propose that the mechanism of the abrupt thinning and retreat of the EAIS along the southern Soya Coast was marine ice-sheet instability caused by mCDW intrusion into deep submarine valleys. Such abrupt ice-sheet thinning and retreat with similar magnitude and timing have also been reported from Enderby Land, East Antarctica. Our findings suggest that abrupt thinning and retreat as a consequence of marine ice-sheet instability and intrusion of mCDW during the Early to Mid-Holocene may have led to rapid ice-surface lowering of hundreds of meters in East Antarctica.

The δD temperature proxy in Antarctic ice cores varies in parallel with CO2 through glacial cycles. However, these variables display a puzzling asynchrony. Well-dated records of Southern Ocean temperature will provide crucial information because the Southern Ocean is likely key in regulating CO2 variations. Here, we perform multiple isotopic analyses on an Antarctic ice core and estimate temperature variations at this site and in the oceanic moisture source over the past 720,000 years, which extend the longest records by 300,000 years. Antarctic temperature is affected by large variations in local insolation that are induced by obliquity. At the obliquity periodicity, the Antarctic and ocean temperatures lag annual mean insolation. Further, the magnitude of the phase lag is minimal during low eccentricity periods, suggesting that secular changes in the global carbon cycle and the ocean circulation modulate the phase relationship among temperatures, CO2 and insolation in the obliquity frequency band.

The mid-latitude westerly winds of the Southern Hemisphere play a central role in the global climate system via Southern Ocean upwelling, carbon exchange with the deep ocean, Agulhas leakage (transport of Indian Ocean waters into the Atlantic) and possibly Antarctic ice-sheet stability. Meridional shifts of the Southern Hemisphere westerly winds have been hypothesized to occur in parallel with the well-documented shifts of the intertropical convergence zone in response to Dansgaard-Oeschger (DO) events - abrupt North Atlantic climate change events of the last ice age. Shifting moisture pathways to West Antarctica are consistent with this view but may represent a Pacific teleconnection pattern forced from the tropics. The full response of the Southern Hemisphere atmospheric circulation to the DO cycle and its impact on Antarctic temperature remain unclear. Here we use five ice cores synchronized via volcanic markers to show that the Antarctic temperature response to the DO cycle can be understood as the superposition of two modes: a spatially homogeneous oceanic bipolar seesaw mode that lags behind Northern Hemisphere climate by about 200 years, and a spatially heterogeneous atmospheric mode that is synchronous with abrupt events in the Northern Hemisphere. Temperature anomalies of the atmospheric mode are similar to those associated with present-day Southern Annular Mode variability, rather than the Pacific-South American pattern. Moreover, deuterium-excess records suggest a zonally coherent migration of the Southern Hemisphere westerly winds over all ocean basins in phase with Northern Hemisphere climate. Our work provides a simple conceptual framework for understanding circum-Antarctic temperature variations forced by abrupt Northern Hemisphere climate change. We provide observational evidence of abrupt shifts in the Southern Hemisphere westerly winds, which have previously documented ramifications for global ocean circulation and atmospheric carbon dioxide. These coupled changes highlight the necessity of a global, rather than a purely North Atlantic, perspective on the DO cycle.

Whereas ice cores from high-accumulation sites in coastal Antarctica clearly demonstrate annual layering, it is debated whether a seasonal signal is also preserved in ice cores from lower-accumulation sites further inland and particularly on the East Antarctic Plateau. In this study, we examine 5 m of early Holocene ice from the Dome Fuji (DF) ice core at a high temporal resolution by continuous flow analysis. The ice was continuously analysed for concentrations of dust, sodium, ammonium, liquid conductivity, and water isotopic composition. Furthermore, a dielectric profiling was performed on the solid ice. In most of the analysed ice, the multi-parameter impurity data set appears to resolve the seasonal variability although the identification of annual layers is not always unambiguous. The study thus provides information on the snow accumulation process in central East Antarctica. A layer counting based on the same principles as those previously applied to the NGRIP (North Greenland Ice core Project) and the Antarctic EPICA (European Project for Ice Coring in Antarctica) Dronning Maud Land (EDML) ice cores leads to a mean annual layer thickness for the DF ice of 3.0 ± 0.3 cm that compares well to existing estimates. The measured DF section is linked to the EDML ice core through a characteristic pattern of three significant acidity peaks that are present in both cores. The corresponding section of the EDML ice core has recently been dated by annual layer counting and the number of years identified independently in the two cores agree within error estimates. We therefore conclude that, to first order, the annual signal is preserved in this section of the DF core. This case study demonstrates the feasibility of determining annually deposited strata on the central East Antarctic Plateau. It also opens the possibility of resolving annual layers in the Eemian section of Antarctic ice cores where the accumulation is estimated to have been greater than in the Holocene.

Water stable isotopes in Greenland ice core data provide key paleoclimatic information, and have been compared with precipitation isotopic composition simulated by isotopically enabled atmospheric models. However, post-depositional processes linked with snow metamorphism remain poorly documented. For this purpose, monitoring of the isotopic composition (δ18O, δD) of near-surface water vapor, precipitation and samples of the top (0.5 cm) snow surface has been conducted during two summers (2011–2012) at NEEM, NW Greenland. The samples also include a subset of 17O-excess measurements over 4 days, and the measurements span the 2012 Greenland heat wave. Our observations are consistent with calculations assuming isotopic equilibrium between surface snow and water vapor. We observe a strong correlation between near-surface vapor δ18O and air temperature (0.85 ± 0.11‰ °C−1 (R = 0.76) for 2012). The correlation with air temperature is not observed in precipitation data or surface snow data. Deuterium excess (d-excess) is strongly anti-correlated with δ18O with a stronger slope for vapor than for precipitation and snow surface data. During nine 1–5-day periods between precipitation events, our data demonstrate parallel changes of δ18O and d-excess in surface snow and near-surface vapor. The changes in δ18O of the vapor are similar or larger than those of the snow δ18O. It is estimated using the CROCUS snow model that 6 to 20% of the surface snow mass is exchanged with the atmosphere. In our data, the sign of surface snow isotopic changes is not related to the sign or magnitude of sublimation or deposition. Comparisons with atmospheric models show that day-to-day variations in near-surface vapor isotopic composition are driven by synoptic variations and changes in air mass trajectories and distillation histories. We suggest that, in between precipitation events, changes in the surface snow isotopic composition are driven by these changes in near-surface vapor isotopic composition. This is consistent with an estimated 60% mass turnover of surface snow per day driven by snow recrystallization processes under NEEM summer surface snow temperature gradients. Our findings have implications for ice core data interpretation and model–data comparisons, and call for further process studies.

Densification of firn at the North Greenland Eemian Ice Drilling (NEEM) camp is investigated using density surrogates: dielectric permittivities ∊v and ∊h at microwave frequencies with electrical fields in the vertical and horizontal planes, respectively. Dielectric anisotropy Δ∊ (= ∊v − ∊h) is then examined as a surrogate for the anisotropic geometry of firn. Its size, fluctuations and mutual correlations are investigated in samples taken at depths from the surface to ~90 m. The initial Δ∊ of ~0.06 appears within the uppermost 0.2 m. After that, Δ∊ decreases rapidly until 21–26 m depth. Below this, Δɛ decreases slowly. Layers with more ions of fluorine, chlorine and some cations deposited between the autumn and the subsequent summer deform preferentially during all these stages. This layered deformation is explained partly by the textural effects initially formed by the seasonal variation of metamorphism, and partly by ions such as fluorine, chlorine and ammonium, which are known to modulate dislocation movement in the ice crystal lattice. Insolation-sensitive microstructure appears to be preserved all the way to the pore close-off, within layers of the summer-to-autumn metamorphism. Like previous authors, we hypothesize that calcium is not the active agent in the reported deformation– calcium correlations.

Sea salts and halogens in aerosols, frost flowers, and brine play an important role in atmospheric chemistry in polar regions. Simultaneous sampling and observations of frost flowers, brine, and aerosol particles were conducted around Siorapaluk in northwestern Greenland during December 2013 to March 2014. Results show that water-soluble frost flower and brine components are sea-salt components (e.g., Na+, Cl−, Mg2+, K+, Ca2+, Br−, and iodine). Concentration factors of sea-salt components of frost flowers and brine relative to seawater were 1.14–3.67. Sea-salt enrichment of Mg2+, K+, Ca2+, and halogens (Cl−, Br−, and iodine) in frost flowers is associated with sea-salt fractionation by precipitation of mirabilite and hydrohalite. High aerosol number concentrations correspond to the occurrence of higher abundance of sea-salt particles in both coarse and fine modes, and blowing snow and strong winds. Aerosol number concentrations, particularly in coarse mode, are increased considerably by release from the sea-ice surface under strong wind conditions. Sulfate depletion by sea-salt fractionation was found to be limited in sea-salt aerosols because of the presence of non-sea-salt (NSS) SO42−. However, coarse and fine sea-salt particles were found to be rich in Mg. Strong Mg enrichment might be more likely to proceed in fine sea-salt particles. Magnesium-rich sea-salt particles might be released from the surface of snow and slush layer (brine) on sea ice and frost flowers. Mirabilite-like and ikaite-like particles were identified only in aerosol samples collected near new sea-ice areas. From the field evidence and results from earlier studies, we propose and describe sea-salt cycles in seasonal sea-ice areas.

To better understand how sea salt reacts in surface snow of Antarctica, we collected and identified non-volatile particles in surface snow along a traverse in East Antarctica. Samples were obtained during summer 2012/2013 from coastal to inland regions within 69°S to 80°S and 39°E to 45°E, a total distance exceeding 800 km. The spatial resolution of samples is about one sample per latitude between 1500 and 3800 m altitude. Here, we obtain the atomic ratios of Na, S and Cl, and calculate the masses of sodium sulphate and sodium chloride. The results show that, even in the coast snow sample (69°S), sea salt is highly modified by acid (HNO 3 or H 2 SO 4 ). The fraction of sea salt that reacts with acid increases in the region from 70°S to 74°S below 3000 m a.s.l., where some NaCl remains. At the higher altitudes (above 3300 m a.s.l.) in the inland region (74°S to 80°S), the reaction uses almost all of the available NaCl. Keywords: sea salt, modification, sodium sulphate, sodium nitrate, single-particle analysis (Published: 5 July 2016) Citation: Tellus B 2016, 68, 29285, http://dx.doi.org/10.3402/tellusb.v68.29285

AbstarctWe conducted a pit study in July 2009 at the NEEM (North Greenland Eemian Ice Drilling) deep ice-coring site in northwest Greenland. To examine the seasonal variations of snow chemistry and characteristics of the drill site, we collected snow/firn samples from the wall of a 2 m deep pit at intervals of 0.03 m and analyzed them for electric conductivity, pH, Cl–, NO3–, SO42–, CH3SO3– (MSA), Na+, K+, Mg2+, Ca2+ and stable isotopes of water (δ18O and δD). Pronounced seasonal variations in the stable isotopes of water were observed, which indicated that the snow had accumulated regularly during the past 4 years. Concentrations of Na+, Cl– and Mg2+, which largely originate from sea salt, peaked in winter to early spring, while Ca2+, which mainly originates from mineral dust, peaked in late winter to spring, slightly later than Na+, Cl– and Mg2+. Concentrations of NO3– showed double peaks, one in summer and the other in winter to spring, whereas those of SO42– peaked in winter to spring. The winter-to-spring concentrations of NO3– and SO42– seem to have been strongly influenced by anthropogenic inputs. Concentrations of MSA showed double peaks, one in spring and the other in late summer to autumn. Our study confirms that the NEEM deep ice core can be absolutely dated to a certain depth by counting annual layers, using the seasonal variations of stable isotopes of water and those of ions. We calculated the annual surface mass balance for the years 2006–08. The mean annual balance was 176 mm w.e., and the balances for winter-to-summer and summer-to-winter halves of the year were 98 and 78 mm, respectively. Snow deposition during the winter-to-summer half of the year was greater than that during the summer-to-winter half by 10–20mm for all three years covered by this study.

Climatic variabilities on millennial and longer time scales with a bipolar seesaw pattern have been documented in paleoclimatic records, but their frequencies, relationships with mean climatic state, and mechanisms remain unclear. Understanding the processes and sensitivities that underlie these changes will underpin better understanding of the climate system and projections of its future change. We investigate the long-term characteristics of climatic variability using a new ice-core record from Dome Fuji, East Antarctica, combined with an existing long record from the Dome C ice core. Antarctic warming events over the past 720,000 years are most frequent when the Antarctic temperature is slightly below average on orbital time scales, equivalent to an intermediate climate during glacial periods, whereas interglacial and fully glaciated climates are unfavourable for a millennial-scale bipolar seesaw. Numerical experiments using a fully coupled atmosphere-ocean general circulation model with freshwater hosing in the northern North Atlantic showed that climate becomes most unstable in intermediate glacial conditions associated with large changes in sea ice and the Atlantic Meridional Overturning Circulation. Model sensitivity experiments suggest that the prerequisite for the most frequent climate instability with bipolar seesaw pattern during the late Pleistocene era is associated with reduced atmospheric CO2 concentration via global cooling and sea ice formation in the North Atlantic, in addition to extended Northern Hemisphere ice sheets., SCOPUS: ar.j, info:eu-repo/semantics/published