[en] We report measurements of pH, total alkalinity, air-ice CO2 fluxes (chamber method) and CaCO3 content of frost flowers (FF) and thin landfast sea ice. As the temperature decreases, concentration of solutes in the brine skim (BS) increases. Along this gradual concentration process, some salts reach their solubility threshold and start precipitating. The precipitation of ikaite (CaCO3.6H2O) was confirmed in the FF and throughout the ice by Raman spectroscopy and X-ray analysis. The amount of ikaite precipitated was estimated to be 25 µmol kg-1 melted FF, in the FF and is shown to decrease from 19 µmol kg-1 to 15 µmol kg-1 melted ice in the upper part and at the bottom of the ice, respectively. CO2 release due to precipitation of CaCO3 is estimated to be 50 µmol kg-1 melted samples. The dissolved inorganic carbon (DIC) normalized to a salinity of 10 exhibits significant depletion in the upper layer of the ice and in the FF. This DIC loss is estimated to be 2069 µmol kg-1 melted sample and corresponds to a CO2 release from the ice to the atmosphere ranging from 20 to 40 mmol m-2 d-1. This estimate is consistent with flux measurements of air-ice CO2 exchange. Our measurements confirm previous laboratory findings that growing young sea ice acts as a source of CO2 to the atmosphere. CaCO3 precipitation during early ice growth appears to promote the release of CO2 to the atmosphere however its contribution to the overall release by newly formed ice is most likely minor.
Alvarez-Aviles, L., W. R. Simpson, T. A. Douglas, M. Sturm, D. Perovich, and F. Domine (2008), Frost flower chemical composition during growth and its implications for aerosol production and bromine activation, J. Geophys. Res., 113, D21304, doi: 10.1029/2008JD010277.
Arrigo, K. R., and C. W. Sullivan (1992), The influence of salinity and temperature covariation on the photophysiological characteristics of Antarctic sea ice microalgae, J. Phycol, 28(6), 746-756. (Pubitemid 24407346)
Arrigo, K. R., T. Mock, and P. M. Lizotte (2010), Primary producers and sea ice, in Sea Ice, 2nd edition, Blackwell Sci., London, pp. 283-326, Oxford.
Assur, A. (1958), Composition of sea ice and its tensile strength, in Arctic Sea Ice, edited by National Academy of Sciences-National Research Council. Easton, Maryland.
Bates, N. R., and J. T. Mathis (2009), The Arctic Ocean marine carbon cycle: Evaluation of air-sea CO2 exchanges, ocean acidification impacts and potential feedbacks, Biogeosciences, 6(11), 2433-2459.
Bischoff, J. L., J. A. Fitzpatrick, and R. J. Rosenbauer (1993a), The solubility and stabilization of ikaite (CaCO3.6H2O) from 0 °C to 25 °C environmental and paleoclimatic implications for Thinolite Tufa, J. Geol., 101(1), 21-33. (Pubitemid 23389217)
Bischoff, J. L., S. Stine, R. J. Rosenbauer, J. A. Fitzpatrick, and T. W. Stafford (1993b), Ikaite precipitation by mixing of shoreline springs and lake water, Mono Lake, California, USA, Geochimica Et Cosmochimica Acta, 57(16), 3855-3865. (Pubitemid 24394655)
Bischoff, W. D., S. K. Sharma, and F. T. Mackenzie (1985), Carbonate ion disorder in synthetic and biogenic magnesian calcites: A Raman spectral study, American Mineralogist, 70, 581-589.
Bowman, J. S., and J. W. Deming (2010), Elevated bacterial abundance and exopolymers in saline frost flowers and implications for atmospheric chemistry and microbial dispersal, Geophys. Res. Lett, 37, L13501, doi: 10.1029/2010GL043020.
Buchardt, B. (2004), Ikaite geochemistry and formation of submarine tufas in Greenland, Geochimica Et Cosmochimica Acta, 68(11), A348-A348.
Buchardt, B., C. Israelson, P. Seaman, and G. Stockmann (2001), Ikaite tufa towers in Ikka Fjord, southwest Greenland: Their formation by mixing of seawater and alkaline spring water, J. Sediment. Res., 71(1), 176-189.
Delille, B. (2006), Inorganic carbon dynamics and air-ice-sea CO2 fluxes in the open and coastal waters of the Southern Ocean, 296 pp, Université de Liège, Liège.
Delille, B., B. Jourdain, A. V. Borges, J. L. Tison, and D. Delille (2007), Biogas (CO2, O-2, dimethylsulfide) dynamics in spring Antarctic fast ice, Limnology and Oceanography, 52(4), 1367-1379. (Pubitemid 47121551)
Deming, J. W. (2010), Sea ice bacteria and viruses, in Sea Ice, 2nd ed, edited by D. N. Thomas and G S. Dieckmann, pp. 1-22, Wiley-Blackwell, Oxford.
Dickson, A. G, and F. J. Millero (1987), A comparison of the equilibrium constants for the dissociation of carbonic acid in seawater media, Deep Sea Research, I(34), 1733-1743.
Dieckmann, G S., G. Nehrke, C. Uhlig, J. Göttlicher, S. Gerland, M. A. Granskog, and D. N. Thomas (2010), Brief communication: Ikaite (CaCO 3.6H2O) discovered in Arctic sea ice, The Cryosphere, 4, 227-230.
Dieckmann, G. S., G. Nehrke, S. Papadimitriou, J. Gottlicher, R. Steininger, H. Kennedy, D. Wolf-Gladrow, and D. N. Thomas (2008), Calcium carbonate as ikaite crystals in Antarctic sea ice, Geophys. Res. Lett, 35, L08501, doi: 10.1029/2008GL033540.
DOE (U.S. Department of Energy) (1994), Handbook of Methods for the Analysis of the Various Parameters of the Carbon Dioxide System in Sea Water, edited by A. G Dickson and C. Goyet, Carbon Dioxide Inofrmation Analysis Center, Oak Ridge National Laboratory, Oak Ridge, Tenn.
Domine, F., A. S. Taillandier, and W. R. Simpson (2005), Specific surface area, density and microstructure of frost flowers, Geophys. Res. Lett, 32, L13502, doi: 10.1029/2005GL023245. (Pubitemid 41319961)
Druckenmiller, M. L., H. Eicken, M. A. Johnson, D. J. Pringle, and C. C. Williams (2009), Toward an integrated coastal sea-ice observatory: System components and a case study at Barrow, Alaska, Cold Regions Science and Technology, 56(2-3), 61-72.
Ehn, J. K., B. J. Hwang, R. Galley, and D. G Barber (2007), Investigations of newly formed sea ice in the Cape Bathurst polynya: 1. Structural, physical, and optical properties, J. Geophys. Res. Oceans, 112, CO5002, doi: 10.1029/2006JC003702.
Eicken, H. (2003), From the microscopic to the macroscopic to the regional scale, growth, microstrucutre and properties of sea ice, in Sea Ice - An Introduction to its Physics, Biology, Chemistry and Geology, edited by D. N Thomas and G S Dieckmann, pp. 22-81, Wiley-Blackwell, Hoboken, N. J.
Frankignoulle, M. (1988), Field-measurements of air sea CO2 exchange, Limnology and Oceanography, 33(3), 313-322.
Frankignoulle, M., and A. V. Borges (2001), Direct and indirect pCO 2 measurements in a wide range of pCO2 and salinity values (the Scheldt estuary), Aquatic Geochemistry, 7(4), 267-273. (Pubitemid 34577523)
Geilfus, N. X., G Carnat, T. N. Papakyriakou, J. L. Tison, B. Else, H. Thomas, E. H. Shadwick, and B. Delille (2012), pCO2 dynamics and related air-ice CO2 fluxes in the Arctic coastal zone (Amundsen Gulf, Beaufort Sea), J. Geophys. Res., 117, C00G10, doi: 10.1029/2011JC007118.
Gleitz, M., M. R. v.d. Loeff, D. N. Thomas, G. S. Dieckmann, and F. J. Millero (1995), Comparison of summer and winter in organic carbon, oxygen and nutrient concentrations in Antarctic sea ice brine, Mar. Chem., 51(2), 81-91.
Golden, K. M., H. Eicken, A. L. Heaton, J. Miner, D. J. Pringle, and J. Zhu (2007), Thermal evolution of permeability and microstructure in sea ice, Geophysical Research Letters, 34, L16501, doi: 10.1029/2007GL030447. (Pubitemid 350065333)
Gosselin, M., M. Levasseur, P. A. Wheeler, R. A. Horner, and B. C. Booth (1997), New measurements of phytoplankton and ice algal production in the Arctic Ocean, Deep Sea Research II, 44(8), 1623-1644. (Pubitemid 28159080)
Gran, G. (1952), Determination of the equivalence point in potentiometric titration, Analyst, Part II(77), 661-671.
Grasshoff, K., M. Ehrhardt, and K. Kremling (1983), Methods of Seawater Analysis, 2nd ed., 419 pp., Verlag Chemie, New York.
Kennedy, G. L., D. M. Hopkins, and W. J. Pickthorn (1987), Ikaite, the glen-donite precursor, in estuarine sediments at Barrow, Arctic Alaska, Geological Survey of Alaska Annual Meeting, Abstract, Programme 9, 725.
Krembs, C., H. Eicken, K. Junge, and J. W. Deming (2002), High concentrations of exopolymeric substances in Arctic winter sea ice: Implications for the polar ocean carbon cycle and cryoprotection of diatoms, Deep-Sea Research Part I-Oceanographic Research Papers, 49(12), 2163-2181. (Pubitemid 36178194)
Lee, S. H., T. E. Whitledge, and S. H. Kang (2008), Spring time production of bottom ice algae in the landfast sea ice zone at Barrow, Alaska, J. Exp. Mar. Biol. Ecol., 367(2), 204-212.
Lepparanta, M. (1993), A review of analytical models of sea-ice growth, Atmos.-Ocean, 31(1), 123-138. (Pubitemid 24393857)
Loose, B., W. R. McGillis, P. Schlosser, D. Perovich, and T. Takahashi (2009), Effects of freezing, growth, and ice cover on gas transport processes in laboratory seawater experiments, Geophys. Res. Lett., 36(5), L05603 doi: 10.1029/2008GL036318.
Marion, G. M. (2001), Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO 2-H2O system, Geochimica Et Cosmochimica Acta, 65(12), 1883-1896.
Mathis, J. T., N. R. Bates, D. A. Hansell, and T. Babila (2009), Net community production in the northeastern Chukchi Sea, Deep-Sea Research Part II-Topical Studies in Oceanography, 56(17), 1213-1222.
Mehrbach, C., C. H. Culberson, J. E. Hawley, and R. M. Pytkowicz (1973), Measurements of the apparent dissociation constants of carbonic acid in sea-water at atmospheric pressure, Limnology and Oceanography, 18, 897-907.
Miller, L., T. Papakyriakou, R. E. Collins, J. Deming, J. Ehn, R. W. Macdonald, A. Mucci, O. Owens, M. Raudsepp, and N. Sutherland (2011), Carbon dynamics in sea ice: A winter flux time series, J. Geophys. Res. Oceans, 116, C02028, doi: 10.1029/2009JC006058.
Morin, S., G. M. Marion, R. von Glasow, D. Voisin, J. Bouchez, and J. Savarino (2008), Precipitation of salts in freezing seawater and ozone depletion events: A status report, Atmos. Chem. Phys., 8(23), 7317-7324.
Munro, D. R., R. B. Dunbar, D. A. Mucciarone, K. R. Arrigo, and M. C. Long (2010), Stable isotope composition of dissolved inorganic carbon and partic-ulate organic carbon in sea ice from the Ross Sea, Antarctica, J. Geophys. Res. Oceans, 115, C09005, doi: 10.1029/2009JC005661.
Nomura, D., H. Yoshikawa-Inoue, and T. Toyota (2006), The effect of sea-ice growth on air-sea CO2 flux in a tank experiment, Tellus Series B-Chemical and Physical Meteorology, 58(5), 418-426. (Pubitemid 44575816)
Nomura, D., H. Yoshikawa-Inoue, T. Toyota, and K. Shirasawa (2010a), Effects of snow, snow-melting and re-freezing processes on air-sea ice CO 2 flux, J. Glaciology, 56(196), 262-270.
Nomura, D., H. Eicken, R. Gradinger, and K. Shirasawa (2010b), Rapid physically driven inversion of the air-sea ice CO2 flux in the seasonal landfast ice off Barrow, Alaska after onset surface melt, Continental Shelf Research, 30(19), 1998-2004.
Papadimitriou, S., H. Kennedy, G. Kattner, G. S. Dieckmann, and D. N. Thomas (2004), Experimental evidence for carbonate precipitation and CO 2 degassing during sea ice formation, Geochimica et Cosmochimica Acta, 68(8), 1749-1761. (Pubitemid 38463105)
Papadimitriou, S., D. N. Thomas, H. Kennedy, C. Haas, H. Kuosa, A. Krell, and G. S. Dieckmann (2007), Biogeochemical composition of natural sea ice brines from the Weddell Sea during early austral summer, Limnology and Oceanography, 52(5), 1809-1823. (Pubitemid 47612110)
Papakyriakou, T., and L. Miller (2011), Springtime CO2 exchange over seasonal sea ice in the Canadian Arctic Archipelago, Annals of Glaciology, 52, 215-224.
Perovich, D. K., and J. A. Richter-Menge (1994), Surface characteristics of lead ice, Journal of Geophysical Research-Oceans, 99(C8), 16341-16350.
Piot, M., and R. von Glasow (2008), The potential importance of frost flowers, recycling on snow, and open leads for ozone depletion events, Atmos. Chem. Phys., 8(9), 2437-2467.
Rankin, A. M., V. Auld, and E. W. Wolff (2000), Frost flowers as a source of fractionated sea salt aerosol in the polar regions, Geophys. Res. Lett., 27(21), 3469-3472.
Rankin, A. M., E. W. Wolff, and S. Martin (2002), Frost flowers: Implications for tropospheric chemistry and ice core interpretation, J. Geophys. Res.-Atmos., 107(D23), 4683, doi: 10.1029/2002JD002492. (Pubitemid 43197276)
Rysgaard, S., R. N. Glud, M. K. Sejr, J. Bendtsen, and P. B. Christensen (2007), Inorganic carbon transport during sea ice growth and decay: A carbon pump in polar seas, J. Geophys. Res. Oceans, 112, C03016, doi: 10.1029/2006JC003572. (Pubitemid 46845222)
Rysgaard, S., J. Bendtsen, L. T. Pedersen, H. Ramlov, and R. N. Glud (2009), Increased CO2 uptake due to sea ice growth and decay in the Nordic Seas, J. Geophys. Res., 114(C09011), doi: 10.1029/2008JC005088.
Sander, R., J. Burrows, and L. Kaleschke (2006), Carbonate precipitation in brine - a potential trigger for tropospheric ozone depletion events, Atmos. Chem. Phys., 6, 4653-4658. (Pubitemid 44600870)
Selleck, B. W., P. F. Carr, and B. G. Jones (2007), A review and synthesis of glendonites (pseudomorphs after ikaite) with new data: Assessing applicability as recorders of ancient coldwater conditions, J. Sediment. Res., 77(11), 980-991. (Pubitemid 350252850)
Semiletov, I. P., A. Makshtas, S. I. Akasofu, and E. L. Andreas (2004), Atmospheric CO2 balance: The role of Arctic sea ice, Geophys. Res. Lett., 31, L05121, doi: 10.1029/2003GL017996.
Semiletov, I. P., I. Pipko, I. Repina, and N. E. Shakhova (2007), Carbonate chemistry dynamics and carbon dioxide fluxes across the atmosphere-ice-water interfaces in the Arctic Ocean: Pacific sector of the Arctic, J. Mar. Syst., 66(1-4), 204-226. (Pubitemid 46694321)
Takahashi, T., et al. (2009), Climatological mean and decadal change in surface ocean pCO2, and net sea-air CO2 flux over the global oceans, Deep-Sea Research Part II-Topical Studies in Oceanography, 56(8-10), 554-577.
Thomas, D. N., S. Papadimitriou, and C. Michel (2010), Biogeochemistry of sea ice, in Sea Ice, 2nd ed., edited by D. N. Thomas and G. S. Dieckmann, p. 621, Wiley-Blackwell, Hoboken, N. J.
Timco, G. W., and R. M. W. Frederking (1996), A review of sea ice density, Cold Regions Science and Technology, 24(1), 1-6.
Tison, J. L., A. Worby, B. Delille, F. Brabant, S. Papadimitriou, D. Thomas, J. de Jong, D. Lannuzel, and C. Haas (2008), Temporal evolution of decaying summer first-year sea ice in the Western Weddell Sea, Antarctica, Deep-Sea Research Part II-Topical Studies in Oceanography, 55(8-9), 975-987.
Weeks, W. F., and S. F. Ackley (1982), The growth, structure, and properties of sea ice., 117 pp., CRREL Monograph.
Whiticar, M. J., and E. Suess (1998), The cold carbonate connection between Mono Lake, California and the Bransfield Strait, Antarctica, Aquatic Geochemistry, 4(3-4), 429-454. (Pubitemid 29199134)
Zemmelink, H. J., B. Delille, J. L. Tison, E. J. Hintsa, L. Houghton, and J. W. H. Dacey (2006), CO2 deposition over the multi-year ice of the western Weddell Sea, Geophys. Res. Lett., 33, L13606, doi: 10.1029/ 2006GL026320. (Pubitemid 44945949)