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Constraining the past sea ice variability in the Nordic Seas is critical for a comprehensive understanding of the abrupt DansgaardOeschger (D-O) climate changes during the last glacial. Here we present unprecedentedly detailed sea ice proxy evidence from two Norwegian Sea sediment cores and an East Greenland ice core to resolve and constrain sea ice variations during four D-O events between 32 and 41 ka. Our independent sea ice records consistently reveal a millennial-scale variability and threshold response between an extensive seasonal sea ice cover in the Nordic Seas during cold stadials and reduced seasonal sea ice conditions during warmer interstadials. They document substantial and rapid sea ice reductions that may have happened within 250 y or less, concomitant with reinvigoration of deep convection in the Nordic Seas and the abrupt warming transitions in Greenland. Our empirical evidence thus underpins the cardinal role of rapid sea ice decline and related feedbacks to trigger abrupt and large-amplitude climate change of the glacial D-O events.

Sunlit snow is highly photochemically active and plays a key role in the exchange of gas phase species between the cryosphere and the atmosphere. Bromine (Br), Iodine (I) and Mercury (Hg) can be photoactivated by the UV radiation and, in certain circumstances, released from the snowpack into the atmosphere. Mercury is a heavy metal with a known toxicity present in the environment in several different chemical forms. Once present in the snowpack, Hg is very labile and, thanks to the UV light, it can be reduced back to elemental Hg (Hg(0)) and undergo dynamic exchange with the atmosphere. Similar to mercury, iodine can undergo photochemical activation in surface snow resulting in its presence in the surrounding atmosphere where it plays a crucial role in new particle formation. Bromine has a central role in the mercury cycle in polar regions (through the Atmospheric mercury depletion events) as well as contributing to the tropospheric ozone cycle in the polar region causing the so-called Ozone depletion events. However, compared to Iodine and Mercury, it seems to be more stable after deposition into the snow pack. Here we present measurements of bromine, iodine and mercury performed by ICP-MS, on snow pit and shallow core samples taken over a 2100 km traverse in East Antarctica from the coast to the interior (Talos Dome – Dome C traverse 2016 and East Antarctic International Ice Sheet Traverse, EAIIST 2019). The shallow core and the snow pit samples at each site are estimated to cover about 10 to 20 years of snow accumulation, giving us a deposition record from approximately the late 90s, to around the early 21st century. The concentrations determined in different sampling sites show a rather clear decrease trend from the coast with the minima as we approach the inner part of the Antarctic plateau. In addition, the analysis of surface and bulk samples from EAIIST show a decrease of concentrations toward the inland except for the sites characterised by a strong snow metamorphosis caused mainly by the wind friction. In almost all the sampling sites of the EAIIST traverse the concentrations of Br, I and Hg increase with sample depth, possibly due to snowpack photochemical activation in the upper part of the snowpack. Future studies are planned to investigate the possible link between the determined concentration profile and the variation of the solar radiation reaching the Antarctic Plateau during spring caused by the ozone hole formation.

17 pags., 4 figs., 2 tabs., Sea ice plays a pivotal role in Earth's climate and its past reconstruction is crucial to investigate the connections and feedbacks with the other components of the climate system. Among the available archives that store information of past sea ice are marine and ice cores. Recent studies on the IP biomarker extracted from marine sediments has shown great skill to infer past changes of Arctic sea ice. In ice matrixes, sodium, bromine and iodine have shown potential to store the fingerprint of sea ice presence. The development of an unambiguous sea ice proxy from ice cores, however, has proven to be a challenging task especially in the Arctic realm. In this work we analyze the sodium, bromine and iodine records in the RECAP ice core, coastal eastern Greenland, to investigate the sea ice variability in the northern North Atlantic Ocean through the last 11,000 years of the current interglacial, i.e. the Holocene. We compare the RECAP records with marine sea ice proxy records available from the northern North Atlantic. We suggest that RECAP sodium concentrations can be associated with variability of sea ice extent, while the bromine-to-sodium ratios and iodine are associated respectively with seasonal sea ice and bioproductivity from open ocean and fresh sea ice surfaces. According to our interpretation, we find that sea ice was at its lowest extent and seasonal in nature during the early Holocene in all regions of the North Atlantic. Increasing sea ice signals are seen from ca. 8–9 ka b2k, in line with long-term Holocene cooling. The increasing sea ice trend appears uninterrupted in the Fram Strait and North Iceland while reaching a maximum ca. 5 ka b2k in the East Greenland region. Sea ice modifications during the last 5000 years display great variability in East Greenland with intermediate conditions between the early and mid Holocene, possibly associated with local fjord dynamics. The last sea ice maximum was reached across all regions 1000 years b2k., The RECAP ice coring effort was financed by the Danish Research Council through a Sapere Aude grant, the NSF through the Division of Polar Programs, the Alfred Wegener Institute, and the European Research Council under the European Community's Seventh Framework Programme (FP7/2007e2013)/ERC grant agreement The RECAP ice coring effort was financed by the Danish Research Council through a Sapere Aude grant, the NSF through the Division of Polar Programs, the Alfred Wegener Institute, and the European Research Council under the European Community's Seventh Framework Programme (FP7/2007e2013)/ERC grant agreement 610055 through the Ice2Ice project. Additional funding support for the paper has been provided by the Centre for Climate Dynamics at the Bjerknes Centre. through the Ice2Ice project. Additional funding support for the paper has been provided by the Centre for Climate Dynamics at the Bjerknes Centre.

Biomass burning influences global atmospheric chemistry by releasing greenhouse gases and climate-forcing aerosols. There is controversy about the magnitude and timing of Holocene changes in biomass burning emissions from millennial to centennial time scales and, in particular, on the possible impact of ancient civilizations. Here we present a 5 kyr record of fire activity proxies levoglucosan, black carbon and ammonium measured in the RECAP ice core, drilled in the coastal East Greenland and therefore affected by processes occurring in the High North Atlantic Region. Levoglucosan and ammonium fluxes show high levels from 5 to 4.5 kyr followed by an abrupt decline, possibly due to monotonic decline in Northern Hemisphere summer insolation. Levoglucosan and black carbon show an abrupt decline at 1.1 kyr BP (before 2000 AD), suggesting a decline in wildfire regime in the Icelandic territory due to the extensive land clearing caused by Viking colonizers. A minimum is reached at 0.5 kyr BP for all fire proxies, after which levoglucosan and ammonium fluxes increase again, in particular over the last 200 years. We find that the fire regime reconstructed from RECAP fluxes seems mainly related to climatic changes, however over the last millennium human activities might have had a substantial influence controlling the occurrence of fire.

41 pags., 25 figs., 5 tabs. 1 app., As the intricacies of paleoclimate dynamics are explored, it is becoming understood that sea-ice variability can instigate, or contribute to, climate change instabilities commonly described as “tipping points”. Compared to ice sheets and circulating ocean currents, sea-ice is ephemeral and continental-scale changes to sea ice cover occur seasonally. Sea-ice greatly influences polar albedo, atmosphere-ocean gas exchange and vertical mixing of polar ocean masses. Major changes in sea ice distribution and thickness have been invoked as drivers of deglaciations as well as stadial climate variability described in Greenland climate records as “Dansgaard-Oeschger” cycles and described in Antarctic climate records as “Antarctic Isotopic Maxima”., The role of halogens in polar atmospheric chemistry has been studied intensively over the past few decades. This research has been driven by the role of bromine, primarily as gas-phase bromine monoxide (BrO), which exerts a key control on polar tropospheric ozone concentrations. Initial findings led to the discovery of boundary-layer self-catalyzing heterogeneous bromine reactions fed by sunlight and ozone, known as bromine explosions. First-year sea-ice and blowing snow have been identified as key components for this heterogeneous bromine recycling in the polar boundary layer. This understanding of polar halogen chemistry – supported by an expanding body of observations and modeling – has formed the basis for investigating quantitative links between halogen concentrations in the polar atmospheric boundary layer and sea-ice presence and/or extent. Despite the clear importance of sea-ice in paleoclimate research, the ice core community lacks a conservative and quantitative proxy for sea-ice extent. The most commonly applied proxy, methanesulphonic acid (MSA), is volatile and has not been demonstrated reliably for ice core records extending beyond the last few centuries. Sodium has also been applied to reconstruct sea-ice extent in a semi-quantitative manner although the effects of meteorological transport noise are significant. Contrary to a priori expectations, the halogens bromine and iodine appear to be stable in polar snow and ice over millennial timescales, addressing the temporal limitations of MSA records. Unfortunately, transport and meteorological variability influence sodium deposition as well as the deposition of halogens and the many other ionic impurities found in ice cores. The atmospheric chemistry of halogens is more complex than those of sodium or MSA due to the mixed-phase (gas and aerosol) nature of halogen photochemistry. Thus the application of halogen records in ice cores to sea-ice reconstruction overcomes some challenges posed by existing proxies, but also opens new challenges specific to halogens. Challenges common to all sea-ice proxies include the deconvolution of changes in emission source locations and changes in transport efficacy, particularly those occurring during climate transitions combining changes in sea-ice and atmospheric circulation, such as stadial/interstadial or glacial/interglacial climate variability., In this review, we describe the rationale and available evidence for linking the halogens bromine and iodine found in polar snow and ice to sea-ice extent. Reported measurements of bromine and iodine in polar snow and ice samples are critically discussed. We also consider aspects of halogen transport and retention in polar snow and ice that are still poorly understood. Overall, there is a growing body of evidence supporting the application of bromine to sea-ice reconstructions, and the use of iodine to reconstruct marine biological activity mediated in part by sea-ice extent. These halogens complement existing sea-ice proxies but most crucially, offer the capacity to greatly extend the temporal and spatial coverage of ice core-based sea-ice reconstructions. We identify knowledge gaps existing in the current understanding of spatial and temporal variability of halogen distributions in the polar regions. We suggest areas where polar halogen chemistry can contribute to a better understanding of the halogen records recovered from ice cores. Finally, we propose future steps for establishing reliable and constructive sea-ice reconstructions based on bromine and iodine as observed in snow and ice cores., This research has received funding from the European Research Council under the European Community's Seventh Framework Programme (FP7/2007–2013)/ERC grant agreement 610055 as part of the ice2ice project. We would like to acknowledge the essential contribution of the Inuit Windsled Project, consisting of Ross Edwards, Hermenegildo Moreno, Jens Jacob Simonsen and Ramon Larramendi, in providing snow samples collecting during the 2017 Kangerlussuaq-EGRIP traverse., The GV7 surface sampling was support by the MIUR (Italian Ministry of University and Research) - PNRA (Italian Antarctic Research Programme) program through the IPICS-2kyr-It project (International Partnership for Ice Core Science, reconstructing the climate variability for the last 2kyr, the Italian contribution). The IPICS-2kyr-It project is carried out in cooperation with KOPRI (Korea Polar Research Institute, grant No. PE15010). The Dome C surface snow sampling was supported by the Programma Nazionale per la Ricerca in Antartide (PNRA, project 650 number 2013/AC3.03 PEA 2013–2015, PI Warren Cairns). The Talos Dome-Dome C traverse and associated analyses was supported by the Programma Nazionale per la Ricerca in Antartide (PNRA), project A2 number PNRA0016_295 “Bromine and mercury, cycles and transport processes on the Antarctic plateau”. We thank the CNR Dirigibile Italia Arctic station and the Department of Earth systems science and environmental technologies for logistical support in Svalbard.

The detection of insoluble particles trapped in ice cores, like volcanic and dust particles, pollen grains, foraminifera and diatom assemblages, represents the experimental basis for multiple lines of environmental paleoresearch regarding the atmosphere, the biosphere and volcanology. To date, except for ice core dust, the detection of such particles is achieved through observations by manual microscopy. Artificial Intelligence predictive models are already applied to several research fields within geoscience, but up to date its implementation to ice core science is missing. The recently EU funded Marie Curie ICELEARNING project (2020-2022) aims to develop a two-phase routine for the automatic quantification of insoluble particles trapped in ice cores. The routine is based on a commercial Flow Imaging Microscope producing micro-scale images of insoluble particles from melted ice core samples. The image collection of mineral dust, tephra, pollen and marine foraminifera obtained from natural and/or ad-hoc prepared samples will constitute the training datasets. The images will be then analyzed by Pattern Recognition algorithms developed for automatic particle classification and counting. The routine will be specifically developed in order to be implemented in ice core Continuous Flow Analysis (CFA) systems, thus improving the more traditional methods and potentially providing continuous ice core insoluble particle records. The ICELEARNING methodology is suitable for melted ice core samples and any diluted aqueous sample, thus representing a ground-breaking analytical advancement for a wide range of research fields, from ice core science to marine geology. The innovative routine here presented is automatic and non-destructive, imperative prerequisites for future Antarctic ice core projects.

The Col Margherita (MRG) Observatory is a high-altitude background station located in the Eastern Italian Alps. Its elevation and distance from major anthropogenic and natural sources make it ideal for monitoring baseline mercury levels and investigating its geochemical cycles. In this work, total gaseous mercury (TGM), ozone (O3) and meteorological variables were studied to investigate seasonal and diurnal variability of TGM measurements from March 2018 to May 2019. We found that the year-round mean TGM concentration was 1.8 times higher than the annual atmospheric mercury measurements previously reported during the GMOS project at the same measurement site. The seasonal variation of TGM was characterized by high values in spring and summer and lower values in winter. A systematic diel pattern of TGM was obtained, with low concentrations during the daytime and higher concentrations in the late evening. Spatial patterns and temporal changes in TGM, back- trajectories (BTs) and planetary boundary layer (PBL) analysis showed that total gaseous mercury levels were influenced by local meteorology, as well as regional and long-range transport of air masses. The lowest TGM concentrations in winter are associated with high wind speeds, low boundary layer height and cleaner air masses originating from the Western sector. Conversely, the highest TGM concentrations in spring and summer were attributed to polluted air masses passing over North-eastern and Continental Europe and were probably favoured by the higher PBL height. During the snow cover season, investigation of TGM peak events also demonstrated the potential influence of re-emission processes of previously reactive mercury deposition over snow surfaces.

The role of deposition fluxes on the mercury cycle at Concordia station, on the high Antarctic plateau have been investigated over the Austral summer between December 2017 to January 2018. Wet/frozen deposition was collected daily from specially sited tables, simultaneously with the collection of surface (0-3 cm) and subsurface (3-6 cm) snow and the analysis of Hg-0 in the ambient air. Over the course of the experiment the atmospheric Hg-0 concentrations ranged from 0.58 +/- 0.19 to 1.00 +/- 0.33 ng m(-3), surface snow Hg concentrations varied between (0-3 cm) 0.006 +/- 0.003 to 0.001 +/- 0.001 ng cm(-3) and subsurface snow (3-6 cm) concentrations varied between 0.001 +/- 0.001 to 0.003 +/- 0.002 ng cm(-3). The maximum daily wet deposition flux was found to be 23 ng m(-2) d(-)(1). Despite the low temporal resolution of our measurements combined with their potential errors, the linear regression of the Hg deposition fluxes against the snow accumulation rates allowed us to estimate the mean dry deposition rate from the intercept of the graph as -0.005 +- 0.008 ng m(-2) d(-1). From this analysis, we conclude that wet deposition accounts for the vast majority of the Hg deposition fluxes at Concordia Station. The number of snow events, together with the continuous GEM measurements have allowed us to make a first estimation of the mean snow scavenging factor at Dome C. Using the slope of the regression of mercury flux on snow accumulation we obtained a snow scavenging factor that ranges from 0.21 to 0.22 +/- 0.02 (ng(Hg)/g (snow))/(ng(Hg)/m(3) (air)). Our data indicate that the boundary layer height and local meteorological effects influence Hg-0 reemission from the top of (0-3 cm) the snowpack into the atmosphere and into the deeper snowpack layer (3-6 cm). These data will help constrain numerical models on the behaviour of mercury in Antarctica.

Dust found in polar ice core samples present extremely low concentrations, in addition the availability of such samples is usually strictly limited. For these reasons the chemical and physical analysis of polar ice cores is an analytical challenge. In this work a new method based on low background instrumental neutron activation analysis (LB-INAA) for the multi-elemental characterization of the insoluble fraction of dust from polar ice cores is presented. Thanks to an accurate selection of the most proper materials and procedures it was possible to reach unprecedented analytical performances, suitable for ice core analyses. The method was applied to Antarctic ice core samples. Five samples of atmospheric dust (μg size) from ice sections of the Antarctic Talos Dome ice core were prepared and analyzed. A set of 37 elements was quantified, spanning from all the major elements (Na, Mg, Al, Si, K, Ca, Ti, Mn and Fe) to trace ones, including 10 (La, Ce, Nd, Sm, Eu, Tb, Ho, Tm, Yb and Lu) of the 14 natural occurring lanthanides. The detection limits are in the range of 10 −13 –10 −6 g, improving previous results of 1–3 orders of magnitude depending on the element; uncertainties lies between 4% and 60%.

Between the end of September and the beginning of October 2017, low but detectable air concentrations of Ruthenium-106 ( R 106 u ) were measured throughout the European atmosphere. To date, the source has not been clearly identified. This study aims at constraining the location of the most likely emission source, by combining HYSPLIT back trajectories and a multi-site source-receptor model. The model follows a concentration weighted trajectory (CWT) approach, based on a R 106 u measurement dataset gathered by the International Atomic Energy Agency (IAEA) shortly after the event and shared by the French Institut de Radioprotection et de Surete Nucleaire (IRSN). The back trajectories are computed using Global Data Assimilation System (GDAS) and ERA-Interim meteorological data, with horizontal resolution from 1.5° to 0.5°. The effect of the starting altitude was also investigated. The source-receptor model results show that the most likely emission source region extends from Ukraine to the West to the Russian Volga and Ural regions to the East, in accordance with two previous studies. The analyses also show that the identified source region is relatively insensitive to the type of meteorological data, their horizontal resolution and values of starting altitude. The model precision is found to increase with increasing number of receptors. The method is fully open-source, requires low computational resources and is therefore suited to estimate the source origin of radioactive pollutants on a real time basis, providing an additional tool to more sophisticated atmospheric models.

The application of instrumental neutron activation analysis (INAA) for multi-elemental analysis of samples of extremely reduced mass such as dust samples extracted from ice cores requires specific efforts towards the development of a “low level counting” analytical technique. An analytical protocol specifically designed for this kind of samples, based on low-background INAA (LBNAA) is here presented. A first application of the method was successfully performed on samples from the new alpine firn core NextData-LYS12. Sub-ng detection limits were reached for many elements. According to this point the technique is also potentially suitable to be applied to polar ice core samples.

The Law Dome site is ideal for the evaluation of sea ice proxies due to its location near to the Antarctic coast, regular and high accumulation throughout the year, an absence of surface melting or remobilization, and minimal multiyear sea ice. We present records of bromine and iodine concentrations and their enrichment beyond seawater compositions and compare these to satellite observations of first-year sea ice area in the 90-130°ĝ€E sector of the Wilkes coast. Our findings support the results of previous studies of sea ice variability from Law Dome, indicating that Wilkes coast sea ice area is currently at its lowest level since the start of the 20th century. From the Law Dome DSS1213 firn core, 26 years of monthly deposition data indicate that the period of peak bromine enrichment is during austral spring-summer, from November to February. Results from a traverse along the lee (western) side of Law Dome show low levels of sodium and bromine deposition, with the greatest fluxes in the vicinity of the Law Dome summit. Finally, multidecadal variability in iodine enrichment appears well correlated to bromine enrichment, suggesting a common source of variability that may be related to the Interdecadal Pacific Oscillation (IPO).