Calibration of Arctic ice core bromine enrichment records for past sea ice reconstructions.

Bromine in ice cores has been proposed as a qualitative sea ice proxy to produce sea ice reconstructions for the polar regions. Here we report the first statistical validation of this proxy with satellite sea ice observations by combining bromine enrichment (with respect to seawater, Brenr) records from three Greenlandic ice cores (SIGMA-A, NU and RECAP) with satellite sea ice imagery, over three decades. We find that during the 1984-2016 satellite-era, ice core Brenr values are significantly correlated with first-year sea ice formed in the Baffin Bay and Labrador Sea supporting that the gas-phase bromine enrichment processes, preferentially occurring over the sea ice surface, are the main driver for the Brenr signal in ice cores. Moreover, in assessing Brenr's capability to record historical sea ice variability, we compare 20th-century Arctic Sea ice historical and proxy records with our reconstructions, based on an autoregressive-moving-average (ARMA) model, finding overall good agreement. While further enhancements are warranted, including site-specific calibrations and a comprehensive investigation into bromine transport-related concerns, this study presents a new method to quantitatively reconstruct past seasonal sea ice variability through bromine enrichment in ice cores.

Characteristics and quantification of small microplastics (<100 µm) in seasonal svalbard snow on glaciers and lands.

Small microplastics (SMPs < 100 µm) can easily be transported over long distances far from their sources through the atmospheric pathways and reach even remote regions, including the Arctic. However, these sizes of MPs are mostly overlooked due to different analytical challenges; besides, their pathways through atmospheric depositions, such as snow depositions, are mostly unknown. The spatial variability in bulk snow samples was investigated for the first time in distinct sites (e.g., glaciers) near Ny Ålesund, the world-known northernmost permanent research settlement in the Svalbard Islands, to better comprehend the presence of SMP pollution in snow. Seasonal snow deposited over the tundra and the summits of different glaciers were also sampled. A sampling procedure was designed to obtain representative samples while minimizing plastic contamination, thanks to rigorous quality assurance and quality control protocol. SMPs' weight (µg SMP L-1) and deposition load (mg SMPs m-2) result from being lower in the remote glaciers, where they may be subject to long-range transport. The SMPs' minimum length was 20 µm, with the majority less than 100 µm. Regarding their size distribution, there was an increase in the size length deriving from the local input of the human presence near the scientific settlement. The presence of some polymers might be site-specific in relation to the pathways that affect their distribution at the sites studied. Also, from the snow surface layer collected at the same sites to evaluate the variability of SMPs during specific atmospheric deposition events, the results confirmed their higher weight and load in surface snow near the scientific settlement compared to the glaciers. The results will enhance the limited knowledge of the SMPs in polar atmospheric compartments and deposition processes.

Untargeted analysis of environmental contaminants in surface snow samples of Svalbard Islands by liquid chromatography-high resolution mass spectrometry.

In recent years, there is increasing attention on the contaminants of emerging concern (CECs), which include plasticizers, flame retardants, industrial chemicals, pharmaceuticals, and personal care products, since they have been detected even far away from pollution sources. The polar regions are not exempt from the presence of anthropogenic contaminants, and they are employed as a model for understanding the pollutant fate and impact. During the 2021 spring campaign, sixteen surface snow samples were collected close to the research station of Ny-Ålesund located on the Spitsbergen Island of the Norwegian Svalbard Archipelago. The samples were extracted by solid-phase extraction and analyzed by liquid chromatography-high-resolution tandem mass spectrometry (LC-HRMS/MS) following an untargeted approach. Compound tentative identification was obtained with the aid of the software Compound Discoverer, using both mass spectral database search and manual validation. Among the 114 compounds identified with a high confidence level in the snow samples, >80 have some commercial or industrial use (drugs, plasticizers, fragrances, etc.), therefore they could be of anthropogenic origin. Nonetheless, a clear contamination trend did not appear in the snow samples collected on eight different days during one month. The comparison with aerosol samples collected in the same area did not help identifying the source, either, since only a few compounds were in common, and they were mainly of natural origin. As such, the analysis of aerosol sample did not support possible long-range transport, also considering that compounds were detected mostly in the coarse fraction.

Sea ice fluctuations in the Baffin Bay and the Labrador Sea during glacial abrupt climate changes.

Sea ice decline in the North Atlantic and Nordic Seas has been proposed to contribute to the repeated abrupt atmospheric warmings recorded in Greenland ice cores during the last glacial period, known as Dansgaard-Oeschger (D-O) events. However, the understanding of how sea ice changes were coupled with abrupt climate changes during D-O events has remained incomplete due to a lack of suitable high-resolution sea ice proxy records from northwestern North Atlantic regions. Here, we present a subdecadal-scale bromine enrichment (Brenr) record from the NEEM ice core (Northwest Greenland) and sediment core biomarker records to reconstruct the variability of seasonal sea ice in the Baffin Bay and Labrador Sea over a suite of D-O events between 34 and 42 ka. Our results reveal repeated shifts between stable, multiyear sea ice (MYSI) conditions during cold stadials and unstable, seasonal sea ice conditions during warmer interstadials. The shift from stadial to interstadial sea ice conditions occurred rapidly and synchronously with the atmospheric warming over Greenland, while the amplitude of high-frequency sea ice fluctuations increased through interstadials. Our findings suggest that the rapid replacement of widespread MYSI with seasonal sea ice amplified the abrupt climate warming over the course of D-O events and highlight the role of feedbacks associated with late-interstadial seasonal sea ice expansion in driving the North Atlantic ocean-climate system back to stadial conditions.

Climate changes modulated the history of Arctic iodine during the Last Glacial Cycle.

Iodine has a significant impact on promoting the formation of new ultrafine aerosol particles and accelerating tropospheric ozone loss, thereby affecting radiative forcing and climate. Therefore, understanding the long-term natural evolution of iodine, and its coupling with climate variability, is key to adequately assess its effect on climate on centennial to millennial timescales. Here, using two Greenland ice cores (NEEM and RECAP), we report the Arctic iodine variability during the last 127,000 years. We find the highest and lowest iodine levels recorded during interglacial and glacial periods, respectively, modulated by ocean bioproductivity and sea ice dynamics. Our sub-decadal resolution measurements reveal that high frequency iodine emission variability occurred in pace with Dansgaard/Oeschger events, highlighting the rapid Arctic ocean-ice-atmosphere iodine exchange response to abrupt climate changes. Finally, we discuss if iodine levels during past warmer-than-present climate phases can serve as analogues of future scenarios under an expected ice-free Arctic Ocean. We argue that the combination of natural biogenic ocean iodine release (boosted by ongoing Arctic warming and sea ice retreat) and anthropogenic ozone-induced iodine emissions may lead to a near future scenario with the highest iodine levels of the last 127,000 years.

Year-round measurements of size-segregated low molecular weight organic acids in Arctic aerosol.

Organic acids in aerosols Earth's atmosphere are ubiquitous and they have been extensively studied across urban, rural and polar environments. However, little is known about their properties, transport, source and seasonal variations in the Svalbard Archipelago. Here, we present the annual trend of organic acids in the aerosol collected at Ny-Ålesund and consider their size-distributions to infer their possible sources and relative contributions. A series of carboxylic acids were detected with a predominance of C2-oxalic acid. Pinic acid and cis-pinonic acid were studied in order to better understand the oxidative and gas-to-particle processes occurred in the Arctic atmosphere. Since the water-soluble organic fraction is mainly composed by organic acids and ions, we investigated how the seasonal variation leads to different atmospheric transport mechanisms, focusing on the chemical variations between the polar night and boreal summer. Using major ions, levoglucosan and MSA, the Positive Matrix Factorization (PMF) identified five different possible sources: a) sea spray; b) marine primary production; c) biomass burning; d) sea ice related process and e) secondary products.

First discrete iron(II) records from Dome C (Antarctica) and the Holtedahlfonna glacier (Svalbard).

Fe(II) is more soluble and bioavailable than Fe(III) species, therefore the investigation of their relative abundance and redox processes is relevant to better assess the supply of bioavailable iron to the ocean and its impact on marine productivity. In this context, we present a discrete chemiluminescence-based method for the determination of Fe(II) in firn matrices. The method was applied on discrete samples from a snow pit collected at Dome C (DC, Antarctica) and on a shallow firn core from the Holtedahlfonna glacier (HDF, Svalbard), providing the first Fe(II) record from both Antarctica and Svalbard. The method showed low detection limits (0.006 ng g-1 for DC and 0.003 ng g-1 for the HDF) and a precision ranging from 3% to 20% RSD. Fe(II) concentrations ranged between the LoD and 0.077 ng g-1 and between the LoD and 0.300 ng g-1 for the Antarctic and Arctic samples, respectively. The Fe(II) contribution with respect to the total dissolved Fe was comparable in both sites accounting, on average, for 5% and 3%, respectively. We found that Fe(II) correctly identified the Pinatubo/Cerro Hudson eruption in the DC record, demonstrating its reliability as volcanic tracer, while, on the HDF core, we provided the first preliminary insight on the processes that might influence Fe speciation in firn matrices (i.e. organic ligands and pH influences).