Photodegradation of bisphenol A in water and ice: identification of products using three photosensitizers.

Bisphenol A (BPA) is a widespread organic micro-pollutant, found in most environments, including alpine and Arctic regions, and several matrices such as waters and aerosols. Polar regions are characterized by periods of intense irradiation with no sunset due to the continuous sunlight, while alpine areas, despite following the day-night cycle of mid-latitudes, also undergo strong irradiation. For such conditions, it is possible that a fraction of the BPA present in snow may degrade through direct photolysis, producing other unknown species with different environmental mobility and possible ecotoxic effects. Furthermore, the snowpack is rich in species (known as photosensitizers) that facilitate indirect photodegradation processes through reactions involving hydroxyl radicals  · OH , singlet oxygen (1O2), excited triplet states of the organic fraction (3CDOM*), and nitrite/nitrate. In this study, we investigated both direct and indirect photodegradation of BPA in the presence of specific photosensitizers producing  · OH , 1O2, 3CDOM*, and NO2- to specifically explore the products of the reaction. The study was conducted in both liquid water and ice, under light and dark conditions. Results, obtained by HPLC-HRMS, revealed that the matrix in which the reaction takes place, in addition to the photosensitizer used, may influence the degradation by-products. This allows for the possibility of distinguishing the reaction environment based on the identified product.

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.

Long-range transport and deposition on the Arctic snowpack of nuclear contaminated particulate matter.

The primary environmental concern related to nuclear power is the production of radioactive waste hazardous to humans and the environment. The main scientific and technological problems to address this are related to the storage and disposal of the nuclear waste and monitoring the dispersion of radioactive species into the environment. In this work, we determined an anomalously high 14C activity, well above the modern natural background, on surface and seasonal snow sampled in early May 2019 on glaciers in the Hornsund fjord area (Svalbard). Due to the lack of local sources, the high snow concentrations of 14C suggest long-range atmospheric transport of nuclear waste particles from lower latitudes, where nuclear power plants and treatment stations are located. The analysis of the synoptic and local meteorological data allowed us to associate the long-range transport of this anomalous 14C concentration to an intrusion event of a warm and humid air mass that likely brought pollutants from Central Europe to the Arctic in late April 2019. Elemental and organic carbon, trace element concentration data, and scanning electron microscopy morphological analysis were performed on the same snow samples to better constrain the transport process that might have led to the high 14C radionuclide concentrations in Svalbard. In particular, the highest 14C values found in the snowpack (> 200 percent of Modern Carbon, pMC) were associated with the lowest OC/EC ratios (< 4), an indication of an anthropogenic industrial source, and with the presence of spherical particles rich in iron, zirconium, and titanium which, altogether, suggest an origin related to nuclear waste reprocessing plants. This study highlights the role of long-range transport in exposing Arctic environments to human pollution. Given that the frequency and intensity of these atmospheric warming events are predicted to increase due to ongoing climate change, improving our knowledge of their possible impact to Arctic pollution is becoming urgent.

Selection processes of Arctic seasonal glacier snowpack bacterial communities.

BACKGROUND: Arctic snowpack microbial communities are continually subject to dynamic chemical and microbial input from the atmosphere. As such, the factors that contribute to structuring their microbial communities are complex and have yet to be completely resolved. These snowpack communities can be used to evaluate whether they fit niche-based or neutral assembly theories. METHODS: We sampled snow from 22 glacier sites on 7 glaciers across Svalbard in April during the maximum snow accumulation period and prior to the melt period to evaluate the factors that drive snowpack metataxonomy. These snowpacks were seasonal, accumulating in early winter on bare ice and firn and completely melting out in autumn. Using a Bayesian fitting strategy to evaluate Hubbell's Unified Neutral Theory of Biodiversity at multiple sites, we tested for neutrality and defined immigration rates at different taxonomic levels. Bacterial abundance and diversity were measured and the amount of potential ice-nucleating bacteria was calculated. The chemical composition (anions, cations, organic acids) and particulate impurity load (elemental and organic carbon) of the winter and spring snowpack were also characterized. We used these data in addition to geographical information to assess possible niche-based effects on snow microbial communities using multivariate and variable partitioning analysis. RESULTS: While certain taxonomic signals were found to fit the neutral assembly model, clear evidence of niche-based selection was observed at most sites. Inorganic chemistry was not linked directly to diversity, but helped to identify predominant colonization sources and predict microbial abundance, which was tightly linked to sea spray. Organic acids were the most significant predictors of microbial diversity. At low organic acid concentrations, the snow microbial structure represented the seeding community closely, and evolved away from it at higher organic acid concentrations, with concomitant increases in bacterial numbers. CONCLUSIONS: These results indicate that environmental selection plays a significant role in structuring snow microbial communities and that future studies should focus on activity and growth. Video Abstract.

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.

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.

Source, timing and dynamics of ionic species mobility in the Svalbard annual snowpack.

Nearly all ice core archives from the Arctic and middle latitudes (such as the Alps), apart from some very high elevation sites in Greenland and the North Pacific, are strongly influenced by melting processes. The increases in the average Arctic temperature has enhanced surface snow melting even of higher elevation ice caps, especially on the Svalbard Archipelago. The increase of the frequency and altitude of winter "rain on snow" events as well as the increase of the length of the melting season have had a direct impact on the chemical composition of the seasonal and permanent snow layers due to different migration processes of water-soluble species, such as inorganic ions. This re-allocation along the snowpack of ionic species could significantly modify the original chemical signal present in the annual snow. This paper aims to give a picture of the evolution of the seasonal snow strata with a daily time resolution to better understand: a) the processes that can influence deposition b) the distribution of ions in annual snow c) the impact of the presence of liquid water on chemical re-distribution within the annual snow pack. Specifically, the chemical composition of the first 100 cm of seasonal snow on the Austre Brøggerbreen Glacier (Spitsbergen, Svalbard Islands, Norway) was monitored daily from the 27th of March to the 31st of May 2015. The experimental period covered almost the entire Arctic spring until the melting season. This unique dataset gives us a daily picture of the snow pack composition, and helps us to understand the behaviour of cations (K+, Ca2+, Na+, Mg2+) and anions (Br-, I-, SO42-, NO3-, Cl-, MSA) in the Svalbard snow pack. We demonstrate that biologically related depositions occur only at the end of the snow season and that rain and melting events have different impacts on the snowpack chemistry.

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).

Rapid reductions and millennial-scale variability in Nordic Seas sea ice cover during abrupt glacial climate changes.

Constraining the past sea ice variability in the Nordic Seas is critical for a comprehensive understanding of the abrupt Dansgaard-Oeschger (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.

Interannual variability of sugars in Arctic aerosol: Biomass burning and biogenic inputs.

The concentrations and particle-size distribution of sugars in Arctic aerosol samples were studied to investigate their potential sources and transport. Sugars are constituents of the water-soluble organic compounds (WSOC) fraction in aerosol particles where some saccharides are used as tracers of Primary Biological Aerosol Particles (PBAPs). Monosaccharides (arabinose, fructose, galactose, glucose, mannose, ribose, xylose), disaccharides (sucrose, lactose, maltose, lactulose), alcohol-sugars (erythritol, mannitol, ribitol, sorbitol, xylitol, maltitol, galactitol) and anhydrosugars (levoglucosan, mannosan and galactosan) were quantified in aerosol samples collected during three different sampling campaigns (spring and summer 2013, spring 2014 and 2015). The mean total concentrations of sugars were 0.4 ± 0.3, 0.6 ± 0.5 and 0.5 ± 0.6 ng m-3 for 2013, 2014 and 2015 spring campaigns, while the mean concentration increased to 3 ± 3 ng m-3 in the summer of 2013. This work identified a reproducibility in the sugars trend during spring, while the summer data in 2013 allowed to us to demonstrate strong local inputs when the ground was free of snow and ice. Furthermore, the study aims to show that the two specific ratios of sorbitol & galactiol to arabinose were diagnostic for the type of biomass that was burnt. This study demonstrates that not only is long-range atmospheric transport significant. But depending on seasonality, local inputs can also play an important role in the chemical composition of sugars in Arctic aerosol.

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.

Free and combined L- and D-amino acids in Arctic aerosol.

Aerosol samples were collected with a high-volume cascade impactor with a 10 day sampling frequency at the Gruvebadet observatory, close to Ny-Ålesund (Svalbard Islands). A total of 42 filters were analyzed for free and combined amino acids, as they are key components of bio-aerosol. This article provides the first investigation of free and combined L- and d-amino acids in Arctic atmospheric particulate matter. The main aim of this study was to determine how these compounds are distributed in size-segregated aerosols after short-range and long-range atmospheric transport and understand the possible sources of amino acids. The total load of free amino acids ranged from 2.0 to 10.8 pmol m-3, while combined amino acids ranged from 5.5 to 18.0 pmol m-3. At these levels amino compounds could play a role in the chemistry of cloud condensation nuclei and fine particles, for example by influencing their buffering capacity and basicity. Free and combined amino acids were mainly found in the fine aerosol fraction (<0.49 µm) and their concentrations could be affect by several sources, the most important of which were biological primary production and biomass burning.

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.

Rapid increase in atmospheric iodine levels in the North Atlantic since the mid-20th century.

Atmospheric iodine causes tropospheric ozone depletion and aerosol formation, both of which have significant climate impacts, and is an essential dietary element for humans. However, the evolution of atmospheric iodine levels at decadal and centennial scales is unknown. Here, we report iodine concentrations in the RECAP ice-core (coastal East Greenland) to investigate how atmospheric iodine levels in the North Atlantic have evolved over the past 260 years (1750-2011), this being the longest record of atmospheric iodine in the Northern Hemisphere. The levels of iodine tripled from 1950 to 2010. Our results suggest that this increase is driven by anthropogenic ozone pollution and enhanced sub-ice phytoplankton production associated with the recent thinning of Arctic sea ice. Increasing atmospheric iodine has accelerated ozone loss and has considerably enhanced iodine transport and deposition to the Northern Hemisphere continents. Future climate and anthropogenic forcing may continue to amplify oceanic iodine emissions with potentially significant health and environmental impacts at global scale.

Feedback mechanisms between snow and atmospheric mercury: Results and observations from field campaigns on the Antarctic plateau.

The Antarctic Plateau snowpack is an important environment for the mercury geochemical cycle. We have extensively characterized and compared the changes in surface snow and atmospheric mercury concentrations that occur at Dome C. Three summer sampling campaigns were conducted between 2013 and 2016. The three campaigns had different meteorological conditions that significantly affected mercury deposition processes and its abundance in surface snow. In the absence of snow deposition events, the surface mercury concentration remained stable with narrow oscillations, while an increase in precipitation results in a higher mercury variability. The Hg concentrations detected confirm that snowfall can act as a mercury atmospheric scavenger. A high temporal resolution sampling experiment showed that surface concentration changes are connected with the diurnal solar radiation cycle. Mercury in surface snow is highly dynamic and it could decrease by up to 90% within 4/6 h. A negative relationship between surface snow mercury and atmospheric concentrations has been detected suggesting a mutual dynamic exchange between these two environments. Mercury concentrations were also compared with the Br concentrations in surface and deeper snow, results suggest that Br could have an active role in Hg deposition, particularly when air masses are from coastal areas. This research presents new information on the presence of Hg in surface and deeper snow layers, improving our understanding of atmospheric Hg deposition to the snow surface and the possible role of re-emission on the atmospheric Hg concentration.

Free amino acids in the Arctic snow and ice core samples: Potential markers for paleoclimatic studies.

The role of oceanic primary production on climate variability has long been debated. Defining changes in past oceanic primary production can help understanding of the important role that marine algae have in climate variability. In ice core research methanesulfonic acid is the chemical marker commonly used for assessing changes in past primary production. However, other organic compounds such as amino acids, can be produced and emitted into the atmosphere during a phytoplankton bloom. These species can be transported and deposited onto the ice cap in polar regions. Here we investigate the correlation between the concentration of chlorophyll-a, marker of marine primary production, and amino acids present in an ice core. For the first time, free l- and d-amino acids in Arctic snow and firn samples were determined by a sensitive and selective analytical method based on liquid chromatography coupled with tandem mass spectrometry. The new method for the determination of free amino acids concentrations was applied to firn core samples collected on April 2015 from the summit of the Holtedahlfonna glacier, Svalbard (N 79'08.424, E 13'23.639, 1120m a.s.l.). The main results of this work are summarized as follows: (1) glycine, alanine and proline, were detected and quantified in the firn core samples; (2) their concentration profiles, compared with that of the stable isotope δ18O ratio, show a seasonal cycling with the highest concentrations during the spring and summer time; (3) back-trajectories and Greenland Sea chlorophyll-a concentrations obtained by satellite measurements were compared with the amino acids profile obtained from ice core samples, this provided further insights into the present results. This study suggests that the amino acid concentrations in the ice samples collected from the Holtedahlfonna glaciers could reflect changes in oceanic phytoplankton abundance.

Canadian Arctic sea ice reconstructed from bromine in the Greenland NEEM ice core.

Reconstructing the past variability of Arctic sea ice provides an essential context for recent multi-year sea ice decline, although few quantitative reconstructions cover the Holocene period prior to the earliest historical records 1,200 years ago. Photochemical recycling of bromine is observed over first-year, or seasonal, sea ice in so-called "bromine explosions" and we employ a 1-D chemistry transport model to quantify processes of bromine enrichment over first-year sea ice and depositional transport over multi-year sea ice and land ice. We report bromine enrichment in the Northwest Greenland Eemian NEEM ice core since the end of the Eemian interglacial 120,000 years ago, finding the maximum extension of first-year sea ice occurred approximately 9,000 years ago during the Holocene climate optimum, when Greenland temperatures were 2 to 3 °C above present values. First-year sea ice extent was lowest during the glacial stadials suggesting complete coverage of the Arctic Ocean by multi-year sea ice. These findings demonstrate a clear relationship between temperature and first-year sea ice extent in the Arctic and suggest multi-year sea ice will continue to decline as polar amplification drives Arctic temperatures beyond the 2 °C global average warming target of the recent COP21 Paris climate agreement.

Bromine isotope ratio measurements in seawater by multi-collector inductively coupled plasma-mass spectrometry with a conventional sample introduction system.

A simple and accurate methodology for Br isotope ratio measurements in seawater by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) with pneumatic nebulization for sample introduction was developed. The Br(+) signals could be measured interference-free at high mass resolution. Memory effects for Br were counteracted using 5 mmol L(-1) of NH4OH in sample, standard, and wash solutions. The major cation load of seawater was removed via cation exchange chromatography using Dowex 50WX8 resin. Subsequent Br preconcentration was accomplished via evaporation of the sample solution at 90 °C, which did not induce Br losses or isotope fractionation. Mass discrimination was corrected for by external correction using a Cl-matched standard measured in a sample-standard bracketing approach, although Sr, Ge, and Se were also tested as potential internal standards for internal correction for mass discrimination. The δ(81)Br (versus standard mean ocean bromide (SMOB)) values thus obtained for the NaBr isotopic reference material NIST SRM 977 and for IRMM BCR-403 seawater certified reference material are in agreement with literature values. For NIST SRM 977, the (81)Br/(79)Br ratio (0.97291) was determined with a precision ≤0.08‰ relative standard deviation (RSD).