Imprint of Arctic sea ice cover in North-Greenland ice cores

Sea ice is a key component of the climate system, since it modifies the surface albedo, the radiation balance, as well as the exchange of heat, moisture and gases between the ocean and the overlying atmosphere. Hence, the reconstruction of sea ice cover before the instrumental era and the industrial times is crucial to understand the evolution of Arctic climate in the last millennium and better predict its future evolution. However, identifying relevant paleo proxies in climate archives related to sea ice cover is not straightforward. Ice cores from polar regions offer great potential to provide high-resolution records of Arctic sea ice variability from chemical impurities such as Bromine species, which were recently proposed as indicators of sea ice extent, although their variability might be modulated by regional influences. We here use Bromine and Bromine enrichment of two ice cores form North Greenland (B17 & B26) and investigate its potential as proxy to reconstruct sea ice extent over the period 1363–1993 AD. Across the instrumental period, a good correlation is observed with the Baffin Bay and the Greenland Sea for B26 and B17 respectively, with both record showing minima corresponding to known Artic warming events such as the 1420 AD (for B17) and 1920–1940 (Early century warming, B17 & B26), together with a strong decline starting in the late 19th century. We simultaneously derived a chemical classification of sea ice-related contributors of ionic species (i.e. blowing snow, frost flowers, open water) utilizing the depletion of SO42− compare to Ca2+, K+ and Mg2+ characterizing sea ice brines and blowing snow as well the excess of Br− and Cl−, characterizing frost flowers, to elucidate the evolution of the different sources. In both B17 and B26 records we observe a strong contribution of blowing snow in the earliest part of the datasets, gradually declining in recent years in favour of open water sources.

Using CALIOP to constrain blowing snow emissions of sea salt aerosols over Arctic and Antarctic sea ice

Sea salt aerosols (SSA) produced on sea ice surfaces by blowing snow events or the lifting of frost flower crystals have been suggested as important sources of SSA during winter over polar regions. The magnitude and relative contribution of blowing snow and frost flower SSA sources, however, remain uncertain. In this study, we use 2007–2009 aerosol extinction coefficients from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) instrument onboard the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) satellite and the GEOS-Chem global chemical transport model to constrain sources of SSA over Arctic and Antarctic sea ice. CALIOP retrievals show elevated levels of aerosol extinction coefficients (10–20 Mm−1) in the lower troposphere (0–2 km) over polar regions during cold months. The standard GEOS-Chem model underestimates the CALIOP extinction coefficients by 50 %–70 %. Adding frost flower emissions of SSA fails to explain the CALIOP observations. With blowing snow SSA emissions, the model captures the overall spatial and seasonal variation of CALIOP aerosol extinction coefficients over the polar regions but underestimates aerosol extinction over Arctic sea ice in fall to early winter and overestimates winter-to-spring extinction over Antarctic sea ice. We infer the monthly surface snow salinity on first-year sea ice required to minimize the discrepancy between CALIOP extinction coefficients and the GEOS-Chem simulation. The empirically derived snow salinity shows a decreasing trend between fall and spring. The optimized blowing snow model with inferred snow salinities generally agrees with CALIOP extinction coefficients to within 10 % over sea ice but underestimates them over the regions where frost flowers are expected to have a large influence. Frost flowers could thus contribute indirectly to SSA production by increasing the local surface snow salinity and, therefore, the SSA production from blowing snow. We carry out a case study of an Arctic blowing snow SSA feature predicted by GEOS-Chem and sampled by CALIOP. Using back trajectories, we link this feature to a blowing snow event that occurred 2 days earlier over first-year sea ice and was also detected by CALIOP.

Using CALIOP to constrain blowing snow emissions of sea salt aerosols over Arctic and Antarctic sea ice

Sea salt aerosols (SSA) produced on sea ice surfaces by blowing snow events or lifting of frost flower crystals have been suggested as important sources of SSA during winter over polar regions. The magnitude and relative contribution of blowing snow and frost flower SSA sources, however, remain uncertain. In this study, we use 2007–2009 aerosol extinction coefficients from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) instrument onboard the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) satellite and the GEOS-Chem global chemical transport model to constrain sources of SSA over Arctic and Antarctic sea ice. CALIOP retrievals show elevated levels of aerosol extinctions (10–20 Mm−1) in the lower troposphere (0–2 km) over polar regions during cold months. The standard GEOS-Chem model underestimates the CALIOP aerosol extinctions by 50–70 %. Adding frost flower emissions of SSA fails to explain the CALIOP observations. With blowing snow SSA emissions, the model captures the overall spatial and seasonal variation of CALIOP aerosol extinctions over the polar regions, but overestimates springtime aerosol extinctions over Arctic sea ice and winter-spring extinctions over Antarctic sea ice. We reduce the surface snow salinity over multi-year sea ice and infer the monthly FYI snow salinity required to minimize the discrepancy between CALIOP extinctions and the GEOS-Chem simulation. The empirically-derived snow salinity shows a decreasing trend in between fall and spring. The optimized blowing snow model with inferred snow salinities generally agrees with CALIOP extinction observations to within 10 % over sea ice, but underestimates aerosol extinctions over the regions where frost flowers are expected to have a large influence. Frost flowers could thus contribute indirectly to SSA production by increasing the local surface snow salinity and, therefore, the SSA production from blowing snow. We carry out a case study of an Arctic blowing snow SSA feature predicted by GEOS-Chem and sampled by CALIOP. Using backtrajectories, we link this feature to a blowing snow event which occurred 2 days earlier over first-year sea ice and was also detected by CALIOP.

Horizontal and vertical structure of reactive bromine events probed by bromine monoxide MAX-DOAS

Heterogeneous photochemistry converts bromide (Br−) to reactive bromine species (Br atoms and bromine monoxide, BrO) that dominate Arctic springtime chemistry. This phenomenon has many impacts such as boundary-layer ozone depletion, mercury oxidation and deposition, and modification of the fate of hydrocarbon species. To study environmental controls on reactive bromine events, the BRomine, Ozone, and Mercury EXperiment (BROMEX) was carried out from early March to mid-April 2012 near Barrow (Utqiaġvik), Alaska. We measured horizontal and vertical gradients in BrO with multiple-axis differential optical absorption spectroscopy (MAX-DOAS) instrumentation at three sites, two mobile and one fixed. During the campaign, a large crack in the sea ice (an open lead) formed pushing one instrument package ∼ 250 km downwind from Barrow (Utqiaġvik). Convection associated with the open lead converted the BrO vertical structure from a surface-based event to a lofted event downwind of the lead influence. The column abundance of BrO downwind of the re-freezing lead was comparable to upwind amounts, indicating direct reactions on frost flowers or open seawater was not a major reactive bromine source. When these three sites were separated by ∼ 30 km length scales of unbroken sea ice, the BrO amount and vertical distributions were highly correlated for most of the time, indicating the horizontal length scales of BrO events were typically larger than ∼ 30 km in the absence of sea ice features. Although BrO amount and vertical distribution were similar between sites most of the time, rapid changes in BrO with edges significantly smaller than this ∼ 30 km length scale episodically transported between the sites, indicating BrO events were large but with sharp edge contrasts. BrO was often found in shallow layers that recycled reactive bromine via heterogeneous reactions on snowpack. Episodically, these surface-based events propagated aloft when aerosol extinction was higher (> 0.1 km−1); however, the presence of aerosol particles aloft was not sufficient to produce BrO aloft. Highly depleted ozone (< 1 nmol mol−1) repartitioned reactive bromine away from BrO and drove BrO events aloft in cases. This work demonstrates the interplay between atmospheric mixing and heterogeneous chemistry that affects the vertical structure and horizontal extent of reactive bromine events.

Frost flowers and sea-salt aerosols over seasonal sea-ice areas in northwestern Greenland during winter–spring

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.

Evaporating brine from frost flowers with electron microscopy and implications for atmospheric chemistry and sea-salt aerosol formation

An environmental scanning electron microscope (ESEM) was used for the first time to obtain well-resolved images, in both temporal and spatial dimensions, of lab-prepared frost flowers (FFs) under evaporation within the chamber temperature range from −5 to −18 °C and pressures above 500 Pa. Our scanning shows temperature-dependent NaCl speciation: the brine covering the ice was observed at all conditions, whereas the NaCl crystals were formed at temperatures below −10 °C as the brine oversaturation was achieved. Finger-like ice structures covered by the brine, with a diameter of several micrometres and length of tens to 100 µm, are exposed to the ambient air. The brine-covered fingers are highly flexible and cohesive. The exposure of the liquid brine on the micrometric fingers indicates a significant increase in the brine surface area compared to that of the flat ice surface at high temperatures; the NaCl crystals formed can become sites of heterogeneous reactivity at lower temperatures. There is no evidence that, without external forces, salty FFs could automatically fall apart to create a number of sub-particles at the scale of micrometres as the exposed brine fingers seem cohesive and hard to break in the middle. The fingers tend to combine together to form large spheres and then join back to the mother body, eventually forming a large chunk of salt after complete dehydration. The present microscopic observation rationalizes several previously unexplained observations, namely, that FFs are not a direct source of sea-salt aerosols and that saline ice crystals under evaporation could accelerate the heterogeneous reactions of bromine liberation.

Wintertime enhancements of sea salt aerosol in polar regions consistent with a sea ice source from blowing snow

Sea salt aerosols (SSA) are generated via air bubbles bursting at the ocean surface as well as by wind mobilization of saline snow and frost flowers over sea-ice-covered areas. The relative magnitude of these sources remains poorly constrained over polar regions, affecting our ability to predict their impact on halogen chemistry, cloud formation, and climate. We implement a blowing snow and a frost flower emission scheme in the GEOS-Chem global chemical transport model, which we validate against multiyear (2001–2008) in situ observations of SSA mass concentrations at three sites in the Arctic, two sites in coastal Antarctica, and from the 2008 ICEALOT cruise in the Arctic. A simulation including only open ocean emissions underestimates SSA mass concentrations by factors of 2–10 during winter–spring for all ground-based and ship-based observations. When blowing snow emissions are added, the model is able to reproduce observed wintertime SSA concentrations, with the model bias decreasing from a range of −80 to −34 % for the open ocean simulation to −2 to +9 % for the simulation with blowing snow emissions. We find that the frost flower parameterization cannot fully explain the high wintertime concentrations and displays a seasonal cycle decreasing too rapidly in early spring. Furthermore, the high day-to-day variability of observed SSA is better reproduced by the blowing snow parameterization. Over the Arctic (> 60° N) (Antarctic, > 60° S), we calculate that submicron SSA emissions from blowing snow account for 1.0 Tg yr−1 (2.5 Tg yr−1), while frost flower emissions lead to 0.21 Tg yr−1 (0.25 Tg yr−1) compared to 0.78 Tg yr−1 (1.0 Tg yr−1) from the open ocean. Blowing snow emissions are largest in regions where persistent strong winds occur over sea ice (east of Greenland, over the central Arctic, Beaufort Sea, and the Ross and Weddell seas). In contrast, frost flower emissions are largest where cold air temperatures and open leads are co-located (over the Canadian Arctic Archipelago, coastal regions of Siberia, and off the Ross and Ronne ice shelves). Overall, in situ observations of mass concentrations of SSA suggest that blowing snow is likely to be the dominant SSA source during winter, with frost flowers playing a much smaller role.

Horizontal and vertical structure of reactive bromine events probed by bromine monoxide MAX-DOAS spectroscopy

Heterogeneous photochemistry converts bromide (Br−) to reactive bromine species (Br atoms and bromine monoxide, BrO) that dominate Arctic springtime chemistry. This phenomenon has many impacts such as boundary-layer ozone depletion, mercury oxidation and deposition, and modification of the fate of hydrocarbon species. To study environmental controls on reactive bromine events, the BRomine, Ozone, and Mercury EXperiment (BROMEX) was carried out from early March to mid April 2012 near Barrow (Utqiaġvik), Alaska. We measured horizontal and vertical gradients in BrO with Multiple-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) instrumentation at three sites, two mobile and one fixed. During the campaign, a large crack in the sea ice (an open lead) formed pushing one instrument package ~ 250 km downwind from Barrow (Utqiaġvik). Convection associated with the open lead converted the BrO vertical structure from a surface-based event to a lofted event downwind of the lead influence. The column abundance of BrO downwind of the re-freezing lead was comparable to upwind amounts indicating direct reactions on frost flowers or open seawater was not a major reactive bromine source. When these three sites were separated by ~ 30 km length scales of unbroken sea ice, the BrO amount and vertical distributions were highly correlated for most of the time, indicating the horizontal length scales of BrO events were typically larger than ~ 30 km in the absence of sea-ice features. Although correlation dominated most of the time, rapid changes in BrO with edges significantly sharper than this ~ 30 km length scale episodically transported between the sites, indicating BrO events were large but with sharp edge contrasts. BrO was often found in shallow layers that recycled reactive bromine via heterogeneous reactions on snowpack. Episodically, these surface-based events propagated aloft, which required enhanced aerosol extinction aloft; however, the presence of aerosol particles aloft was not sufficient to produce BrO aloft. Highly depleted ozone (