CO2 and CH4 in sea ice from a subarctic fjord under influence of riverine input

We present the CH4 concentration [CH4], the partial pressure of CO2 (pCO2) and the total gas content in bulk sea ice from subarctic, land-fast sea ice in the Kapisillit fjord, Greenland. Fjord systems are characterized by freshwater runoff and riverine input and based on dδ18O data, we show that > 30% of the surface water originated from periodic river input during ice growth. This resulted in fresher sea-ice layers with higher gas content than is typical from marine sea ice. The bulk ice [CH4] ranged from 1.8 to 12.1 nmol Lg-1, which corresponds to a partial pressure ranging from 3 to 28 ppmv. This is markedly higher than the average atmospheric methane content of 1.9 ppmv. Evidently most of the trapped methane within the ice was contained inside bubbles, and only a minor portion was dissolved in the brines. The bulk ice pCO2 ranged from 60 to 330 ppmv indicating that sea ice at temperatures above -4 °C is undersaturated compared to the atmosphere (390 ppmv). This study adds to the few existing studies of CH4 and CO2 in sea ice, and we conclude that subarctic seawater can be a sink for atmospheric CO2, while being a net source of CH4

Evidence of Freezing Pressure in Sea Ice Discrete Brine Inclusions and Its Impact on Aqueous-Gaseous Equilibrium

Sea ice in part controls surface water properties and the ocean-atmosphere exchange of greenhouse gases at high latitudes. In sea ice, gas exists dissolved in brine and as air bubbles contained in liquid brine inclusions or as bubbles trapped directly within the ice matrix. Current research on gas dynamics within the ocean-sea ice-atmosphere interface has been based on the premise that brine with dissolved air becomes supersaturated with respect to the atmosphere during ice growth. Based on Henry's law, gas bubbles within brine should grow when brine reaches saturation during cooling, given that the total partial pressure of atmospheric gases is above the implicit pressure in brine of 1 atm. Using high-resolution light microscopy time series imagery of gas bubble evolution inside discrete brine pockets, we observed bubbles shrinking during cooling events in response to the development of freezing pressure above 3 atm. During warming of discrete brine pockets, existing bubbles expand and new bubbles nucleate in response to depressurization. Pressure variation within these inclusions has direct impacts on aqueous-gaseous equilibrium, indicating that Henry's law at a constant pressure of 1 atm is inadequate to assess the partitioning between dissolved and gaseous fractions of gas in sea ice. This new evidence of pressure build-up in discrete brine inclusions controlling the solubility of gas and nucleation of bubbles in these inclusions has the potential to affect the transport pathways of air bubbles and dissolved gases within sea ice-ocean-atmosphere interface and modifies brine biochemical properties

Inorganic carbon dynamics of melt-pond-covered first-year sea ice in the Canadian Arctic

Melt pond formation is a common feature of spring and summer Arctic sea ice, but the role and impact of sea ice melt and pond formation on both the direction and size of CO2 fluxes between air and sea is still unknown. Here we report on the CO2-carbonate chemistry of melting sea ice, melt ponds and the underlying seawater as well as CO2 fluxes at the surface of first-year landfast sea ice in the Resolute Passage, Nunavut, in June 2012. Early in the melt season, the increase in ice temperature and the subsequent decrease in bulk ice salinity promote a strong decrease of the total alkalinity (TA), total dissolved inorganic carbon (T CO2) and partial pressure of CO2 (pCO2) within the bulk sea ice and the brine. As sea ice melt progresses, melt ponds form, mainly from melted snow, leading to a low in situ melt pond pCO2 (36 μatm). The percolation of this low salinity and low pCO2 meltwater into the sea ice matrix decreased the brine salinity, TA and T CO2, and lowered the in situ brine pCO2 (to 20 μatm). This initial low in situ pCO2 observed in brine and melt ponds results in air-ice CO2 fluxes ranging between -0.04 and -5.4 mmolm-2 day-1 (negative sign for fluxes from the atmosphere into the ocean). As melt ponds strive to reach pCO2 equilibrium with the atmosphere, their in situ pCO2 increases (up to 380 μatm) with time and the percolation of this relatively high concentration pCO2 meltwater increases the in situ brine pCO2 within the sea ice matrix as the melt season progresses. As the melt pond pCO2 increases, the uptake of atmospheric CO2 becomes less significant. However, since melt ponds are continuously supplied by meltwater, their in situ pCO2 remains undersaturated with respect to the atmosphere, promoting a continuous but moderate uptake of CO2 (∼-1 mmolm-2 day-1) into the ocean. Considering the Arctic seasonal sea ice extent during the melt period (90 days), we estimate an uptake of atmospheric CO2 of -10.4 Tg of Cyr-1. This represents an additional uptake of CO2 associated with Arctic sea ice that needs to be further explored and considered in the estimation of the Arctic Ocean's overall CO2 budget

Replacement of multiyear sea ice and changes in the open water season duration in the Beaufort Sea since 2004

The last decade has witnessed the nine lowest Arctic September sea ice extents in the observational record. It also forms the most recent third of the long-term trend in that record, which reached -13.4% decade-1 in 2015. While hemispheric analyses paint a compelling picture of sea ice loss across the Arctic, the situation with multiyear ice in the Beaufort Sea is particularly dire. This study was undertaken in light of substantial changes that have occurred in the extent of summer multiyear sea ice in the Arctic inferred from the passive microwave record. To better elucidate these changes at a sub-regional scale, we use data from the Canadian Ice Service archive, the most direct observations of sea ice stage-of-development available. We also build upon the only previous sea ice climatological analysis for Canada's western Arctic region by sea ice stage-of-development that ended in 2004. The annual evolution of sea ice by stage of development in Canada's western Arctic changed dramatically between 1983 and 2014. The rate of these changes and their spatial prevalence were most prominent in the last decade. In summer, total sea ice loss occurred via reductions in old and first-year sea ice over increasingly large areas and over more months per year. Resultant delay of thermodynamic freeze up has increased the annual open water duration in the study region. The winter sea ice cover was increasingly composed of first-year sea ice at the expense of old ice. Breakup timing has not significantly changed in the region

Imaging air volume fraction in sea ice using non-destructive X-ray tomography

Although the presence of a gas phase in sea ice creates the potential for gas exchange with the atmosphere, the distribution of gas bubbles and transport of gases within the sea ice are still poorly understood. Currently no straightforward technique exists to measure the vertical distribution of air volume fraction in sea ice. Here, we present a new fast and non-destructive X-ray computed tomography technique to quantify the air volume fraction and produce separate images of air volume inclusions in sea ice. The technique was performed on relatively thin (4–22cm) sea ice collected from an experimental ice tank. While most of the internal layers showed air volume fractions 5 mm). While micro bubbles were the most abundant type of gas bubbles, most of the air porosity observed resulted from the presence of large and macro bubbles. The ice texture (granular and columnar) as well as the permeability state of ice are important factors controlling the air volume fraction. The technique developed is suited for studies related to gas transport and bubble migration

Estimates of ikaite export from sea ice to the underlying seawater in a sea ice-seawater mesocosm

The precipitation of ikaite and its fate within sea ice is still poorly understood.We quantify temporal inorganic carbon dynamics in sea ice from initial formation to its melt in a sea ice.seawater mesocosm pool from 11 to 29 January 2013. Based on measurements of total alkalinity (TA) and total dissolved inorganic carbon (TCO2), the main processes affecting inorganic carbon dynamics within sea ice were ikaite precipitation and CO2 exchange with the atmosphere. In the underlying seawater, the dissolution of ikaite was the main process affecting inorganic carbon dynamics. Sea ice acted as an active layer, releasing CO2 to the atmosphere during the growth phase, taking up CO2 as it melted and exporting both ikaite and TCO2 into the underlying seawater during the whole experiment. Ikaite precipitation of up to 167 μmolkg-1 within sea ice was estimated, while its export and dissolution into the underlying seawater was responsible for a TA increase of 64.66 μmolkg-1 in the water column. The export of TCO2 from sea ice to the water column increased the underlying seawater TCO2 by 43.5 μmolkg-1, suggesting that almost all of the TCO2 that left the sea ice was exported to the underlying seawater. The export of ikaite from the ice to the underlying seawater was associated with brine rejection during sea ice growth, increased vertical connectivity in sea ice due to the upward percolation of seawater and meltwater flushing during sea ice melt. Based on the change in TA in the water column around the onset of sea ice melt, more than half of the total ikaite precipitated in the ice during sea ice growth was still contained in the ice when the sea ice began to melt. Ikaite crystal dissolution in the water column kept the seawater pCO2 undersaturated with respect to the atmosphere in spite of increased salinity, TA and TCO2 associated with sea ice growth. Results indicate that ikaite export from sea ice and its dissolution in the underlying seawater can potentially hamper the effect of oceanic acidification on the aragonite saturation state (ωaragonite) in fall and in winter in ice-covered areas, at the time when ωaragonite is smallest

Temporal dynamics of ikaite in experimental sea ice

Ikaite (CaCO3 · 6H2O) is a metastable phase of calcium carbonate that normally forms in a cold environment and/or under high pressure. Recently, ikaite crystals have been found in sea ice, and it has been suggested that their precipitation may play an important role in air-sea CO 2 exchange in ice-covered seas. Little is known, however, of the spatial and temporal dynamics of ikaite in sea ice. Here we present evidence for highly dynamic ikaite precipitation and dissolution in sea ice grown at an outdoor pool of the Sea-ice Environmental Research Facility (SERF) in Manitoba, Canada. During the experiment, ikaite precipitated in sea ice when temperatures were below -4 °C, creating three distinct zones of ikaite concentrations: (1) a millimeter-to-centimeter-thin surface layer containing frost flowers and brine skim with bulk ikaite concentrations of >2000 μmol kg-1, (2) an internal layer with ikaite concentrations of 200-400 μmol kg -1, and (3) a bottom layer with ikaite concentrations of <100 μmol kg-1. Snowfall events caused the sea ice to warm and ikaite crystals to dissolve. Manual removal of the snow cover allowed the sea ice to cool and brine salinities to increase, resulting in rapid ikaite precipitation. The observed ikaite concentrations were on the same order of magnitude as modeled by FREZCHEM, which further supports the notion that ikaite concentration in sea ice increases with decreasing temperature. Thus, varying snow conditions may play a key role in ikaite precipitation and dissolution in sea ice. This could have a major implication for CO2 exchange with the atmosphere and ocean that has not been accounted for previously

Polar oceans and sea ice in a changing climate

Polar oceans and sea ice cover 15% of the Earth’s ocean surface, and the environment is changing rapidly at both poles. Improving knowledge on the interactions between the atmospheric and oceanic realms in the polar regions, a Surface Ocean–Lower Atmosphere Study (SOLAS) project key focus, is essential to understanding the Earth system in the context of climate change. However, our ability to monitor the pace and magnitude of changes in the polar regions and evaluate their impacts for the rest of the globe is limited by both remoteness and sea-ice coverage. Sea ice not only supports biological activity and mediates gas and aerosol exchange but can also hinder some in-situ and remote sensing observations. While satellite remote sensing provides the baseline climate record for sea-ice properties and extent, these techniques cannot provide key variables within and below sea ice. Recent robotics, modeling, and in-situ measurement advances have opened new possibilities for understanding the ocean–sea ice–atmosphere system, but critical knowledge gaps remain. Seasonal and long-term observations are clearly lacking across all variables and phases. Observational and modeling efforts across the sea-ice, ocean, and atmospheric domains must be better linked to achieve a system-level understanding of polar ocean and sea-ice environments. As polar oceans are warming and sea ice is becoming thinner and more ephemeral than before, dramatic changes over a suite of physicochemical and biogeochemical processes are expected, if not already underway.These changes in sea-ice and ocean conditions will affect atmospheric processes by modifying the production of aerosols, aerosol precursors, reactive halogens and oxidants, and the exchange of greenhouse gases. Quantifying which processes will be enhanced or reduced by climate change calls for tailored monitoring programs for high-latitude ocean environments. Open questions in this coupled system will be best resolved by leveraging ongoing international and multidisciplinary programs, such as efforts led by SOLAS, to link research across the ocean–sea ice–atmosphere interface

Investigating the uptake and fate of poly- and perfluoroalkylated substances (PFAS) in sea ice using an experimental sea ice chamber

Poly- and perfluoroalkyl substances (PFAS) are contaminants of emerging Arctic concern and are present in the marine environments of the polar regions. Their input to and fate within the marine cryosphere are poorly understood. We conducted a series of laboratory experiments to investigate the uptake, distribution, and release of 10 PFAS of varying carbon chain length (C4–C12) in young sea ice grown from artificial seawater (NaClsolution). We show that PFAS are incorporated into bulk sea ice during ice formation and regression analyses for individual PFAS concentrations in bulk sea ice were linearly related to salinity (r2 = 0.30 to 0.88, n = 18, p < 0.05). This shows that their distribution is strongly governed by the presence and dynamics of brine (high salinity water) within the sea ice. Furthermore, long-chain PFAS (C8–C12), were enriched in bulk ice up to 3-fold more than short-chain PFAS (C4–C7) and NaCl. This suggests that chemical partitioning of PFAS between the different phases of sea ice also plays a role in their uptake during its formation. During sea ice melt, initial meltwater fractions were highly saline and predominantly contained short-chain PFAS, whereas the later, fresher meltwater fractions predominantly contained long-chain PFAS. Our results demonstrate that in highly saline parts of sea ice (near the upper and lower interfaces and in brine channels) significant chemical enrichment (ε) of PFAS can occur with concentrations in brine channels greatly exceeding those in seawater from which it forms (e.g., for PFOA, εrinebrine = 10 ± 4). This observation has implications for biological exposure to PFAS present in brine channels, a common feature of first-year sea ice which is the dominant ice type in a warming Arctic