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The sea ice microstructure is permeated by brine channels and pockets that contain concentrated seawater-derived brine. Cooling the sea ice results in further formation of pure ice within these pockets as thermal equilibrium is attained, resulting in a smaller volume of increasingly concentrated residual brine. The coupled changes in temperature and ionic composition result in supersaturation of the brine with respect to mirabilite (Na2SO4·10H2O) at temperatures below −6.38 °C, which consequently precipitates within the sea ice microstructure. Here, mirabilite solubility in natural and synthetic seawater derived brines, representative of sea ice at thermal equilibrium, has been measured in laboratory experiments between 0.2 and −20.6 °C, and hence we present a detailed examination of mirabilite dynamics within the sea ice system. Below −6.38 °C mirabilite displays particularly large changes in solubility as the temperature decreases, and by −20.6 °C its precipitation results in 12.90% and 91.97% reductions in the total dissolved Na+ and SO42− concentrations respectively, compared to that of conservative seawater concentration. Such large non-conservative changes in brine composition could potentially impact upon the measurement of sea ice brine salinity and pH, whilst the altered osmotic conditions may create additional challenges for the sympagic organisms that inhabit the sea ice system. At temperatures above −6.38 °C, mirabilite again displays large changes in solubility that likely aid in impeding its identification in field samples of sea ice. Our solubility measurements display excellent agreement with that of the FREZCHEM model, which was therefore used to supplement our measurements to colder temperatures. Measured and modelled solubility data were incorporated into a 1D model for the growth of first-year Arctic sea ice. Model results ultimately suggest that mirabilite has a near ubiquitous presence in much of the sea ice on Earth, and illustrate the spatial and temporal evolution of mirabilite within sea ice as it grows throughout an Arctic winter, reaching maximum concentrations of 2.3 g kg−1.

Although salt rejection from sea ice is a key process in deep-water formation in ice-covered seas, the concurrent rejection of CO(2) and the subsequent effect on air-sea CO(2) exchange have received little attention. We review the mechanisms by which sea ice directly and indirectly controls the air-sea CO(2) exchange and use recent measurements of inorganic carbon compounds in bulk sea ice to estimate that oceanic CO(2) uptake during the seasonal cycle of sea-ice growth and decay in ice-covered oceanic regions equals almost half of the net atmospheric CO(2) uptake in ice-free polar seas. This sea-ice driven CO(2) uptake has not been considered so far in estimates of global oceanic CO(2) uptake. Net CO(2) uptake in sea-ice-covered oceans can be driven by; (1) rejection during sea-ice formation and sinking of CO(2)-rich brine into intermediate and abyssal oceanic water masses, (2) blocking of air-sea CO(2) exchange during winter, and (3) release of CO(2)-depleted melt water with excess total alkalinity during sea-ice decay and (4) biological CO(2) drawdown during primary production in sea ice and surface oceanic waters.

The kinetics of calcium carbonate hexahydrate (ikaite) precipitation and dissolution were investigated in seawater and seawater-derived brines at sub-zero temperatures using the constant addition experimental technique. The steady state rate of these two processes was found to be a function of the deviation of the solution from equilibrium with respect to ikaite and conformed to the same empirical rate law as the anhydrous CaCO3 polymorphs, calcite and aragonite. In addition to the saturation state of the brine with respect to ikaite, the salinity of the brine and the temperature of the reaction evidently exerted some control on the ikaite precipitation kinetics, while the dissolution kinetics of the polymorph were not noticeably influenced by these two parameters. The experimental salinity and temperature conditions were equivalent to those at thermal equilibrium between brine and ice in the sea ice cover of polar seas. Simple modelling of the CO2 system by extrapolation of the oceanic equivalent to sea ice brines showed that the physical concentration of seawater ions and the changes in ikaite solubility as a function of salinity and temperature, both inherent in the sea ice system, would be insufficient to drive the emergent brines to ikaite supersaturation and precipitation in sea ice down to −8°C. The loss of dissolved inorganic carbon to the gas phase of sea ice and to sympagic autotrophs are two independent mechanisms which, in nature, could prompt the brine CO2 system towards ikaite supersaturation and precipitation. Under these conditions, the steady state precipitation rate of ikaite was found to be fast enough for rapid formation within short time scales (days to weeks) in sea ice. The observed ikaite dissolution kinetics were also found conducive to short turn-over time scales of a few hours to a few days in corrosive solutions, such as surface seawater.

Over the past two decades, with recognition that the ocean’s sea-ice cover is neither insensitive to climate change nor a barrier to light and matter, research in sea-ice biogeochemistry has accelerated significantly, bringing together a multi-disciplinary community from a variety of fields. This disciplinary diversity has contributed a wide range of methodological techniques and approaches to sea-ice studies, complicating comparisons of the results and the development of conceptual and numerical models to describe the important biogeochemical processes occurring in sea ice. Almost all chemical elements, compounds, and biogeochemical processes relevant to Earth system science are measured in sea ice, with published methods available for determining biomass, pigments, net community production, primary production, bacterial activity, macronutrients, numerous natural and anthropogenic organic compounds, trace elements, reactive and inert gases, sulfur species, the carbon dioxide system parameters, stable isotopes, and water-ice-atmosphere fluxes of gases, liquids, and solids. For most of these measurements, multiple sampling and processing techniques are available, but to date there has been little intercomparison or intercalibration between methods. In addition, researchers collect different types of ancillary data and document their samples differently, further confounding comparisons between studies. These problems are compounded by the heterogeneity of sea ice, in which even adjacent cores can have dramatically different biogeochemical compositions. We recommend that, in future investigations, researchers design their programs based on nested sampling patterns, collect a core suite of ancillary measurements, and employ a standard approach for sample identification and documentation. In addition, intercalibration exercises are most critically needed for measurements of biomass, primary production, nutrients, dissolved and particulate organic matter (including exopolymers), the CO2 system, air-ice gas fluxes, and aerosol production. We also encourage the development of in situ probes robust enough for long-term deployment in sea ice, particularly for biological parameters, the CO2 system, and other gases.