Gas chromatography-mass spectrometry selected ion monitoring and gas chromatography-tandem mass spectrometry selected reaction monitoring analyses of mono-, di- and tri-unsaturated C25 highly branched isoprenoid alkene biomarkers in sea ice and sediment samples: A comparative study.

RATIONALE: The efficiency of selected ion monitoring (SIM) and selected reaction monitoring (SRM) analyses for the quantification of three mono-, di- and tri-unsaturated highly branched isoprenoid (HBI) alkenes (IP25 , IPSO25 and HBI III, respectively), often used as proxies for the occurrence of Arctic and Antarctic sea ice or the adjacent open waters, was compared. METHODS: Gas chromatography (GC)-mass spectrometry (MS)/SIM and GC/MS/MS/SRM analyses were carried out on dilute solutions made from purified standards of these three HBIs, and then on hydrocarbon fractions of several sediment and sea ice sample extracts. More efficient and specific SRM transitions were selected after collision-induced dissociation of each precursor ion at different collision energies. RESULTS: SRM analysis avoided any overestimation of IP25 resulting from the contribution of the coeluting 13 C mass isotopomer of IPSO25 (M+ ˙ + 2) to the SIM target ion. In contrast, SRM analysis is less reliable for IPSO25 quantification in cases where several regio-isomers are present, likely due to intense double bond migrations following electron impact. In the case of HBI III, SRM analysis constitutes a potentially suitable alternative to SIM analysis, especially in terms of improving limit of detection. CONCLUSIONS: Despite the intense migrations of HBI double bonds under electron ionization, the selected SRM transitions should be more suitable than SIM target ions for IP25 and HBI III quantification in complex hydrocarbon fractions of natural samples. However, the advantage is less evident for IPSO25 due to the presence of numerous regio-isomers.

Regime shift in Arctic Ocean sea ice thickness.

Manifestations of climate change are often shown as gradual changes in physical or biogeochemical properties1. Components of the climate system, however, can show stepwise shifts from one regime to another, as a nonlinear response of the system to a changing forcing2. Here we show that the Arctic sea ice regime shifted in 2007 from thicker and deformed to thinner and more uniform ice cover. Continuous sea ice monitoring in the Fram Strait over the last three decades revealed the shift. After the shift, the fraction of thick and deformed ice dropped by half and has not recovered to date. The timing of the shift was preceded by a two-step reduction in residence time of sea ice in the Arctic Basin, initiated first in 2005 and followed by 2007. We demonstrate that a simple model describing the stochastic process of dynamic sea ice thickening explains the observed ice thickness changes as a result of the reduced residence time. Our study highlights the long-lasting impact of climate change on the Arctic sea ice through reduced residence time and its connection to the coupled ocean-sea ice processes in the adjacent marginal seas and shelves of the Arctic Ocean.

Unprecedented decline of Arctic sea ice outflow in 2018.

Fram Strait is the major gateway connecting the Arctic Ocean and North Atlantic Ocean, where nearly 90% of the sea ice export from the Arctic Ocean takes place. The exported sea ice is a large source of freshwater to the Nordic Seas and Subpolar North Atlantic, thereby preconditioning European climate and deep water formation in the North Atlantic Ocean. Here we show that in 2018, the ice export through Fram Strait showed an unprecedented decline since the early 1990s. The 2018 ice export was reduced to less than 40% relative to that between 2000 and 2017. The minimum export is attributed to regional sea ice-ocean processes driven by an anomalous atmospheric circulation over the Atlantic sector of the Arctic. The result indicates that a drastic change of the Arctic sea ice outflow and its environmental consequences happen not only through Arctic-wide ice thinning, but also by regional scale atmospheric anomalies.

Anthropogenic particles in sediment from an Arctic fjord.

The research on plastic pollution is increasing worldwide but little is known about the contamination levels in the Arctic by microplastics and other anthropogenic particles (APs) such as dyed fibres. In this study, two different sampling designs were developed to collect 68 sediment subsamples in five locations in a remote Arctic fjord, Kongsfjorden, northwest of Svalbard. Those five stations composed a transect from a sewage outlet recently installed close to the northernmost settlement, Ny-Ålesund, to an offshore site. Plastics and other APs were extracted by density separation and analysed by both Raman and Fourier Transform Infrared spectroscopy. Among the 37 APs found, 19 were microplastics. The others were classified as APs due to the presence of a dye or another additive. On average, 0.33 AP 100 g-1 were found in the surface sediment and their sizes ranged between 0.10 and 6.31 mm. The site most polluted by APs was located at the mouth of the fjord while the less polluted ones were the offshore and the outlet sites. We believe that currents in the fjord have carried APs towards the mouth of the fjord where an eddy could retain APs which might sink the seafloor due to various reasons (ingestion & packaging, fouling-induced changes in buoyancy). In the cores, several different APs were found down to a depth of 12 cm. These APs may have been present in the sediments for decades or been transported deeper by biota. Here we provided data on plastic but also on other anthropogenic particles from a remote fjord in Svalbard.

Atmospheric deposition of polychlorinated biphenyls to seasonal surface snow at four glacier sites on Svalbard, 2013-2014.

During spring 2014 we collected annual surface snow from four glacial sites on Svalbard, an archipelago in the European Arctic. The sampling sites are 230 km apart from west to east, but are at varying elevations, affecting local atmospheric contaminant inputs. Samples were analyzed for 209 polychlorinated biphenyl (PCB) congeners. The western sites, Holtedahlfonna and Kongsvegen, had the highest ∑PCB flux (26.7 pg cm-2 yr-1 at Kongsvegen) while the lowest was at Lomonosovfonna, in central Svalbard (14.4 pg cm-2 yr-1). The greatest difference between sites was the trichlorobiphenyl homologue which was nearly four times greater at Kongsvegen than the eastern site at Austfonna. The most concentrated congeners at each site were PCB-52, 70 + 74, 95, 101, 110 comprising 32-39% of ∑PCB, similar to Clophen 40 which is comprised 27% of these congeners. Similar variance of these congeners in samples and Clophen 40 was verified by principal components analysis. Air mass back trajectories from likely source areas for all sites were similar, indicating no difference in frequency or distribution of PCB from long-distances, suggesting local PCB sources contributing to Kongsvegen. We found 2,3-DiCB (PCB-5) and 3,3'-DiCB (PCB-11) at all sites; neither was found in western commercial PCB mixtures. PCB-5 may be from the Russian PCB product "Trichlorobiphenyl" or is residue from production of pigment violet 23. PCB-11 may come from waste incineration in northern Europe containing various pigments. These results, in comparison to earlier data from Lomonosovfonna, suggest that PCB inputs are variable and are not declining over time.

Winter storms accelerate the demise of sea ice in the Atlantic sector of the Arctic Ocean.

A large retreat of sea-ice in the 'stormy' Atlantic Sector of the Arctic Ocean has become evident through a series of record minima for the winter maximum sea-ice extent since 2015. Results from the Norwegian young sea ICE (N-ICE2015) expedition, a five-month-long (Jan-Jun) drifting ice station in first and second year pack-ice north of Svalbard, showcase how sea-ice in this region is frequently affected by passing winter storms. Here we synthesise the interdisciplinary N-ICE2015 dataset, including independent observations of the atmosphere, snow, sea-ice, ocean, and ecosystem. We build upon recent results and illustrate the different mechanisms through which winter storms impact the coupled Arctic sea-ice system. These short-lived and episodic synoptic-scale events transport pulses of heat and moisture into the Arctic, which temporarily reduce radiative cooling and henceforth ice growth. Cumulative snowfall from each sequential storm deepens the snow pack and insulates the sea-ice, further inhibiting ice growth throughout the remaining winter season. Strong winds fracture the ice cover, enhance ocean-ice-atmosphere heat fluxes, and make the ice more susceptible to lateral melt. In conclusion, the legacy of Arctic winter storms for sea-ice and the ice-associated ecosystem in the Atlantic Sector lasts far beyond their short lifespan.

Younger Dryas ice margin retreat triggered by ocean surface warming in central-eastern Baffin Bay.

The transition from the last ice age to the present-day interglacial was interrupted by the Younger Dryas (YD) cold period. While many studies exist on this climate event, only few include high-resolution marine records that span the YD. In order to better understand the interactions between ocean, atmosphere and ice sheet stability during the YD, more high-resolution proxy records from the Arctic, located proximal to ice sheet outlet glaciers, are required. Here we present the first diatom-based high-resolution quantitative reconstruction of sea surface conditions from central-eastern Baffin Bay, covering the period 14.0-10.2 kyr BP. Our record reveals warmer sea surface conditions and strong interactions between the ocean and the West Greenland ice margin during the YD. These warmer conditions were caused by increased Atlantic-sourced water inflow combined with amplified seasonality. Our results emphasize the importance of the ocean for ice sheet stability under the current changing climate.

Deposition history of polychlorinated biphenyls to the Lomonosovfonna Glacier, Svalbard: a 209 congener analysis.

A 37 m deep ice core representing 1957-2009 and snow from 2009 to 2010 were collected on the Lomonosovfonna glacier, Svalbard (78.82° N; 17.43° E) and analyzed for 209 polychlorinated biphenyl (PCB) congeners using high-resolution mass spectrometry. Congener profiles in all samples showed the prevalence of tetra- and pentachlorobiphenyls, dominated in all samples by PCB-44, PCB-52, PCB-70 + PCB-74, PCB-87 + PCB-97, PCB-95, PCB-99, PCB-101, and PCB-110. The ∑PCB flux varied over time, but the peak flux, ∼19 pg cm(-2) year(-1) from 1957 to 1966, recurred in 1974-1983, 1998-2009, and 2009-2010. The minimum was 5.75 pg cm(-2) year(-1) in 1989-1998, following a 15 year decline. Peak ∑PCB fluxes here are lower than measured in the Canadian Arctic. The analysis of all 209 congeners revealed that PCB-11 (3,3'-dichlorobiphenyl) was present in all samples, representing 0.9-4.5% of ∑PCB. PCB-11 was not produced in a commercial PCB product, and its source to the Arctic has not been well-characterized; however, our results confirm that the sources to Lomonosovfonna have been active since 1957. The higher fluxes of ∑PCB correspond to periods when average 5 day air mass back trajectories have a frequency of 8-10% and reach 60° N or beyond over northern Europe and western Russia or the North Sea into the U.K.