Abstract. The precipitation of ikaite (CaCO 3 ·6H 2 O) in polar sea ice is critical to the efficiency of the sea ice-driven carbon pump and potentially important to the global carbon cycle, yet the spatial and temporal occurrence of ikaite within the ice is poorly known. We report unique observations of ikaite in unmelted ice and vertical profiles of ikaite abundance and concentration in sea ice for the crucial season of winter. Ice was examined from two locations: a 1 m thick land-fast ice site and a 0.3 m thick polynya site, both in the Young Sound area (74 • N, 20 • W) of NE Greenland. Ikaite crystals, ranging in size from a few µm to 700 µm, were observed to concentrate in the interstices between the ice platelets in both granular and columnar sea ice. In vertical sea ice profiles from both locations, ikaite concentration determined from image analysis, decreased with depth from surface-ice values of 700-900 µmol kg −1 ice (∼25 × 10 6 crystals kg −1 ) to values of 100-200 µmol kg −1 ice (1-7 × 10 6 crystals kg −1 ) near the sea ice-water interface, all of which are much higher (4-10 times) than those reported in the few previous studies. Direct measurements of total alkalinity (TA) in surface layers fell within the same range as ikaite concentration, whereas TA concentrations in the lower half of the sea ice were twice as high. This depth-related discrepancy suggests interior ice processes where ikaite crystals form in surface sea ice layers and partly dissolve in layers below. Melting of sea ice and dissolution of observed concentrations of ikaite would result in meltwater with a pCO 2 of <15 µatm. This value is far below atmospheric values of 390 µatm and surface water concentrations of 315 µatm. Hence, the meltwater increases the potential for seawater uptake of CO 2 .

Abstract.A major issue of Arctic marine science is to understand whether the Arctic Ocean is, or will be, a source or sink for air-sea CO 2 exchange. This has been complicated by the recent discoveries of ikaite (a polymorph of CaCO 3 ·6H 2 O) in Arctic and Antarctic sea ice, which indicate that multiple chemical transformations occur in sea ice with a possible effect on CO 2 and pH conditions in surface waters. Here, we report on biogeochemical conditions, microscopic examinations and x-ray diffraction analysis of single crystals from a melting 1.7 km 2 (0.5-1 m thick) drifting ice floe in the Fram Strait during summer. Our findings show that ikaite crystals are present throughout the sea ice but with larger crystals appearing in the upper ice layers. Ikaite crystals placed at elevated temperatures disintegrated into smaller crystallites and dissolved. During our field campaign in late June, melt reduced the ice floe thickness by 0.2 m per week and resulted in an estimated 3.8 ppm decrease of pCO 2 in the ocean surface mixed layer. This corresponds to an air-sea CO 2 uptake of 10.6 mmol m −2 sea ice d −1 or to 3.3 ton km −2 ice floe week −1 . This is markedly higher than the estimated primary production within the ice floe of 0.3-1.3 mmol m −2 sea ice d −1 . Finally, the presence of ikaite in sea ice and the dissolution of the mineral during melting of the sea ice and mixing of the melt water into the surface oceanic mixed layer accounted for half of the estimated pCO 2 uptake.

[1] Although gypsum has been predicted to precipitate in sea ice, it has never been observed. Here we provide the first report on gypsum precipitation in both experimental and natural sea ice. Crystals were identified by X-ray diffraction analysis. Based on their apparent distinguishing characteristics, the gypsum crystals were identified as being authigenic. The FREeZing CHEMistry (FREZCHEM) model results support our observations of both gypsum and ikaite precipitation at typical in situ sea ice temperatures and confirms the "Gitterman pathway" where gypsum is predicted to precipitate. The occurrence of authigenic gypsum in sea ice during its formation represents a new observation of precipitate formation and potential marine deposition in polar seas.

Abstract. A major issue of Arctic marine science is to understand whether the Arctic Ocean is, or will be, a source or sink for air-sea CO2 exchange. This has been complicated by the recent discoveries of ikaite (CaCO3·6H2O) in Arctic and Antarctic sea ice, which indicate that multiple chemical transformations occur in sea ice with a possible effect on CO2 and pH conditions in surface waters. Here we report on biogeochemical conditions, microscopic examinations and x-ray diffraction analysis of single crystals from an actively melting 1.7 km2 (0.5–1 m thick) drifting ice floe in the Fram Strait during summer. Our findings show that ikaite crystals are present throughout the sea ice but with larger crystals appearing in the upper ice layers. Ikaite crystals placed at elevated temperatures gradually disintegrated into smaller crystallites and dissolved. During our field campaign in late June, melt reduced the ice flow thickness by ca. 0.2 m per week and resulted in an estimated 1.6 ppm decrease of pCO2 in the ocean surface mixed layer. This corresponds to an air-sea CO2 uptake of 11 mmol m−2 sea ice d−1 or to 3.5 ton km−2 ice floe week−1.

The precipitation of ikaite (CaCO₃·6H₂O) in polar sea ice is critical to the efficiency of the sea ice-driven carbon pump and potentially important to the global carbon cycle, yet the spatial and temporal occurrence of ikaite within the ice is poorly known. We report unique observations of ikaite in unmelted ice and vertical profiles of ikaite abundance and concentration in sea ice for the crucial season of winter. Ice was examined from two locations: a 1 m thick land-fast ice site and a 0.3 m thick polynya site, both in the Young Sound area (74° N, 20° W) of NE Greenland. Ikaite crystals, ranging in size from a few µm to 700 µm were observed to concentrate in the interstices between the ice platelets in both granular and columnar sea ice. In vertical sea-ice profiles from both locations, ikaite concentration determined from image analysis, decreased with depth from surfaceice values of 700–900 µmol kg⁻¹ ice (~ 25 × 10⁶ crystals kg⁻¹) to bottom-layer values of 100–200 µmol kg⁻¹ ice (1–7 × 10⁶ kg⁻¹), all of which are much higher (4–10 times) than those reported in the few previous studies. Direct measurements of total alkalinity (TA) in surface layers fell within the same range as ikaite concentration whereas TA concentrations in bottom layers were twice as high. This depth-related discrepancy suggests interior ice processes where ikaite crystals form in surface sea ice layers and partly dissolved in bottom layers. From these findings and model calculations we relate sea ice formation and melt to observed pCO₂ conditions in polar surface waters, and hence, the air-sea CO₂ flux