Hybrid Targeted/Untargeted Screening Method for the Determination of Wildfire and Water-Soluble Organic Tracers in Ice Cores and Snow.

Wildfires can influence the earth's radiative forcing through the emission of biomass-burning aerosols. To better constrain the impacts of wildfires on climate and understand their evolution under future climate scenarios, reconstructing their chemical nature, assessing their past variability, and evaluating their influence on the atmospheric composition are essential. Ice cores are unique to perform such reconstructions representing archives not only of past biomass-burning events but also of concurrent climate and environmental changes. Here, we present a novel methodology for the quantification of five biomass-burning proxies (syringic acid, vanillic acid, vanillin, syringaldehyde, and p-hydroxybenzoic acid) and one biogenic emission proxy (pinic acid) using solid phase extraction (SPE) and ultrahigh-performance liquid chromatography coupled with high-resolution mass spectrometry. This method was also optimized for untargeted screening analysis to gain a broader knowledge about the chemical composition of organic aerosols in ice and snow samples. The method provides low detection limits (0.003-0.012 ng g-1), high recoveries (74 ± 10%), and excellent reproducibility, allowing the quantification of the six proxies and the identification of 313 different molecules, mainly constituted by carbon, hydrogen, and oxygen. The effectiveness of two different sample storage strategies, i.e., re-freezing of previously molten ice samples and freezing of previously loaded SPE cartridges, was also assessed, showing that the latter approach provides more reproducible results.

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.

Antarctic ozone hole modifies iodine geochemistry on the Antarctic Plateau.

Polar stratospheric ozone has decreased since the 1970s due to anthropogenic emissions of chlorofluorocarbons and halons, resulting in the formation of an ozone hole over Antarctica. The effects of the ozone hole and the associated increase in incoming UV radiation on terrestrial and marine ecosystems are well established; however, the impact on geochemical cycles of ice photoactive elements, such as iodine, remains mostly unexplored. Here, we present the first iodine record from the inner Antarctic Plateau (Dome C) that covers approximately the last 212 years (1800-2012 CE). Our results show that the iodine concentration in ice remained constant during the pre-ozone hole period (1800-1974 CE) but has declined twofold since the onset of the ozone hole era (~1975 CE), closely tracking the total ozone evolution over Antarctica. Based on ice core observations, laboratory measurements and chemistry-climate model simulations, we propose that the iodine decrease since ~1975 is caused by enhanced iodine re-emission from snowpack due to the ozone hole-driven increase in UV radiation reaching the Antarctic Plateau. These findings suggest the potential for ice core iodine records from the inner Antarctic Plateau to be as an archive for past stratospheric ozone trends.

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).

Fe2+ in ice cores as a new potential proxy to detect past volcanic eruptions.

Volcanic eruptions are widely used in ice core science to date or synchronize ice cores. Volcanoes emit large amounts of SO2 that is subsequently converted in the atmosphere into sulfuric acid/sulphate. Its discrete and continuous quantification is currently used to determine the ice layers impacted by volcanic emissions, but available high-resolution sulphate quantification methods in ice core (Continuous Flow Analysis (CFA)) struggle with insufficient sensitivity. Here, we present a new high-resolution CFA chemiluminescence method for the continuous determination of Fe2+ species in ice cores that shows clear Fe2+ peaks concurrent with volcanic sulphate peaks in the ice core record. The method, applied on a Greenland ice core, correctly identifies all volcanic eruptions from between 1588 to 1611 and from 1777 to 1850. The method has a detection limit of ∽5 pg g-1 and a quadratic polynomial calibration range of up to at least 1760 pg g-1. Our results show that Fe2+ is a suitable proxy for identifying past volcanic events.

Fragrances and PAHs in snow and seawater of Ny-Ålesund (Svalbard): Local and long-range contamination.

Polar regions are fragile ecosystems threatened by both long-range pollution and local human contamination. In this context, the environmental distribution of the Personal Care Products (PCPs) represent a major knowledge gap. Following preliminary Antarctic studies, Fragrance Materials (FMs) were analyzed in the seawater and snow collected in the area of Ny-Ålesund, Svalbard, to investigate local and long-range contamination. Polycyclic Aromatic Hydrocarbons (PAHs), including Retene, were determined in parallel to help the identification of the governing processes. Concentrations of FMs up to 72 ng L-1 were detected in the surface snow near the settlement and at increasing distances, in relation to the prevailing winds. PAHs follow a similar scheme, with levels of Retene up to 1.8 µg L-1, likely deriving from the occurrence of this compound in the coal dust due to the previous mining activities in the area. The snow seasonal deposition of FMs and PAHs was estimated in a snowpit dug at the top of the Austre Brøggerbreen glacier, indicating the long-range atmospheric transport (LRAT) of these compounds.