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Chemical analysis of sea ice vein μ-environments using Raman spectroscopy

Published online by Cambridge University Press:  16 January 2014

Robert E. Barletta
Affiliation:
Department of Chemistry, University of South Alabama, Mobile, AL 36688, USA ([email protected])
Heather M. Dikes
Affiliation:
Department of Chemistry, University of South Alabama, Mobile, AL 36688, USA ([email protected])

Abstract

Sea ice is a unique environment providing a vast habitat for a variety of life, including microscopic organisms. It accounts for roughly 5–6% of the surface area of the oceans. It is a complex porous structure of crystalline water, gas bubbles, and pockets of brine, as well as a connected structure composed of macro- and micro-porosity filled with concentrated aqueous liquids. Using micro-Raman spectroscopy, it is possible to characterise features of ice at a spatial resolution of a few to tens of micrometers, the scale of relevance to trapped microorganisms, by providing information concerning the presence and amount of molecular species present in the trapped liquids. We have applied this technique to determine the spatial distribution of sulphate, phosphate and carbonate anions in sea-ice veins using ice obtained from the vicinity of the Palmer Station, Antarctica. The observed sulphate concentrations were approximately 20–30% higher than nominal surface seawater concentrations, consistent with the concentration of brine in vein and inclusion liquids during the ice formation process. This concentration was lower than that in veins present in laboratory-prepared ice. Carbonate and dibasic phosphate anions were also observed in the sea ice. This speciation is consistent with an alkaline environment in the sea-ice aqueous system. The mean dibasic phosphate concentration found throughout the sample was 648 mM, while, for carbonate, it was 485 mM. However, these anions showed extremely high spatial variability. The high phosphate and carbonate enhancements observed relative to sulphate point to the influence of processes other than brine formation controlling the chemistry of these anions in sea ice.

Type
Research Article
Copyright
Copyright © Cambridge University Press 2014 

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References

Anderson, L.G. and Jones, P. E.. 1985. Measurements of total alkalinity, calcium, and sulfate in natural sea ice. Journal of Geophysical Research (Oceans) 90: 91949198.Google Scholar
Barletta, R.E. and Roe, C.H.. 2012. Chemical analysis of ice vein μ-environments. Polar Record 48: 334341.Google Scholar
Barletta, R.E., Gros, B.N. and Herring, M.P.. 2009. Analysis of marine biogenic sulfur compounds using Raman spectroscopy: dimethyl sulfide and methane sulfonic acid. Journal of Raman Spectroscopy 40: 972981.Google Scholar
Barletta, R.E., Priscu, J.C., Mader, H.M., Jones, W.L. and Roe, C.H.. 2012. Chemical analysis of ice vein μ-environments II – Analysis of glacial samples from Greenland and Antarctica. Journal of Glaciology 58: 11091118.Google Scholar
Boetius, A., Albrecht, S., Bakker, K., Bienhold, C., Felden, J., Fernandez-Mendez, M., Hendricks, S., Katlein, C., Lalande, C., Krumpen, T., Nicolaus, M., Peeken, I., Rabe, B., Rogacheva, A., Rybakova, E., Somavilla, R., Wenzhofer, F. and RV Polarstern ARK27-3-shipboard science party. 2013. Export of algal biomass from the melting Arctic sea ice. Science 339: 14301432.Google Scholar
Charlson, J.R., Lovelock, J.E., Andreae, M.O. and Warren, S.G.. 1987. Oceanic phytoplankton, atmospheric sulphur, cloud albedo, and climate. Nature 326: 665–661.Google Scholar
Eicken, H. 1992. The role of sea ice in structuring Antarctic ecosystems. Polar Biology 12: 313.Google Scholar
Fransson, A., Chierici, M., Yager, P.L. and Smith, W.O. Jr., 2011. Antarctic sea ice carbon dioxide system and controls. Journal of Geophysical Research (Oceans) 116: C12035-1-C12035-18.Google Scholar
Frezzotti, M.L., Tecce, F. and Casagli, A.. 2012. Raman spectroscopy for fluid inclusion analysis. Journal of Geochemical Exploration 112: 120.CrossRefGoogle Scholar
Geilfus, N.X., Carnat, G., Dieckmann, G.S., Halden, N., Nehrke, G., Papakyriakou, T., Tison, J.L. and Delille, B.. 2013. First estimates of the contribution of CaCO3 precipitation to the release of CO2 to the atmosphere during young sea ice growth. Journal of Geophysical Research (Oceans) 118: 244255.CrossRefGoogle Scholar
Gleitz, M., van der Loeff, R.M., Thomas, N.D., Dieckmann, G.S. and Millero, F.J.. 1995. Sea ice winter inorganic carbon, oxygen and nutrient concentrations in Antarctic sea ice. Marine Chemistry 51: 8191.Google Scholar
Guglielmo, L., Carrada, G.C., Catalano, G., Cozzi, S., DellAnno, A., Fabiano, M., Granata, A., Lazzara, L., Lorenzelli, R., Manganaro, A., Mangoni, O., Misic, C., Modigh, M., Pusceddu, A. and Saggiomo, V.. 2004. Biogeochemistry and algal communities in the annual sea ice at Terra Nova Bay (Ross Sea, Antarctica). Chemistry and Ecology 20: 4355.Google Scholar
Ianoul, A., Coleman, T. and Asher, S.A.. 2002. UV resonance Raman spectroscopic detection of nitrate and nitrite in wastewater treatment processes. Analytical Chemistry 74: 14581461.Google Scholar
Jeffery, N., Hunke, E.C., Elliott, S.M. and Turner, A.. 2012. Biogeochemistry in Sea Ice: CICE model developments. (17th Annual CESM Workshop, Breckenridge CO, May 2012).Google Scholar
Jeffery, N., Hunke, E.C. and Elliott, S.M.. 2011. Modeling the transport of passive tracers in sea ice. Journal of Geophysical Research 116: C07020.Google Scholar
Jones, K.A., Ingham, M. and Eicken, H.. 2012. Modeling the anisotropic brine microstructure in first-year Arctic sea ice. Journal of Geophysical Research 117: C02005.Google Scholar
Junge, K., Krembs, C., Deming, J., Stierle, A. and Eicken, H.. 2001. A microscopic approach to investigate bacteria under in situ conditions in sea-ice samples. Annals of Glaciology 33: 304310.Google Scholar
Kester, D.R. and Pytkowicz, R.M.. 1969. Determination of the apparent dissociation constants of phosphoric acid in seawater. Limnology and Oceanography 12: 243252.CrossRefGoogle Scholar
Kester, D.R., Duedall, I.W., Connors, D.N. and Pytkowicz, R.M.. 1967. Preparation of artificial seawater. Limnology and Oceanography 12: 176179.Google Scholar
Miller, L.A., Papakyriakou, T.N., Collins, R.E., Deming, J.W., Ehn, J.K., Macdonald, R.W., Mucci, A., Owens, O., Raudsepp, M. and Sutherland, N.. 2011. Carbon dynamics in sea ice: a winter flux time series. Journal of Geophysical Research 116: C02028.Google Scholar
Millero, F.J., Graham, T.B., Huang, F., Bustos-Serrano, H. and Pierrot, D.. 2006. Dissociation constants of carbonic acid in seawater as a function of salinity and temperature. Marine Chemistry 100: 8094.Google Scholar
Mock, T. 2002. In situ primary production in young Antarctic sea ice. Hydrobiolgia 470: 127132.Google Scholar
Mock, T. and Gradinger, R.. 1999. Determination of Arctic ice algal production with a new in situ incubation technique. Marine Ecology Progress Series 177: 1526.CrossRefGoogle Scholar
NDIC. 2012. All about sea ice. Boulder: National Snow and Ice Data Center (NDIC), digital media. URL: http://nsidc.org/cryosphere/seaice/characteristics/difference.html (accessed 1 September 2012).Google Scholar
Nedashkovskii, A.P., Khvedynich, S.V. and Petrovskii, T.V.. 2008. Phosphates and silicates in sea ice of the high-latitudinal Arctic: data of the North Pole-34 drifting ice station. Oceanology 48: 646655.Google Scholar
Nomura, D., Assmy, P., Nehrke, G., Granskog, M.A., Fischer, M., Dieckmann, G.S., Fransson, A., Hu, Y. and Schnetger, B.. 2013. Characterization of ikaite (CaCO3·6H2O) crystals in first-year Arctic sea ice north of Svalbard. Annals of Glaciology 54: 125131.Google Scholar
Nomura, D., Nishioka, J., Granskog, M.A., Krell, A., Matoba, S., Toyota, T., Hattori, H. and Shirasawa, K.. 2010. Nutrient distributions associated with snow and sediment-laden layers in sea ice of the southern Sea of Okhotsk. Marine Chemistry 119: 18.Google Scholar
Olson, R.J. 1980. Nitrate and ammonium uptake in Antarctic waters. Limnology and Oceanography 25: 10641074.Google Scholar
Parmentier, F.-J.W., Christensen, T.R., Sørensen, L.L., Rysgaard, S., McGuire, A.D., Miller, P.A. and Walker, D.A.. 2013. The impact of lower sea-ice extent on Arctic greenhouse-gas exchange. Nature Climate Change 3: 195202.Google Scholar
Petrich, C., and Eicken, H.. 2010. Growth, structure and properties of sea ice. In: Thomas, D.N. and Dieckmann, G.S. (editors). Sea ice. Chichester: Wiley-Blackwell: 2377.Google Scholar
Priscu, J.C., Christner, B.C., Foreman, C.M. and Royston-Bishop, G.. 2007. Biological material in ice cores. Encyclopedia of Quaternary Sciences 2: 11561166.Google Scholar
Quinn, P.K. and Bates, T.S.. 2011. The case against climate regulation via oceanic phytoplankton sulphur emissions. Nature 480: 5156.Google Scholar
Rysgaard, S., Bendtsen, J., Delille, B., Dieckmann, G.S., Glud, R.N., Kennedy, H., Mortensen, J., Papadimitriou, S., Thomas, D.N. and Tison, J.-L.. 2011. Sea ice contribution to the air–sea CO2 exchange in the Arctic and Southern Oceans. Tellus B 63: 823830.Google Scholar
Rysgaard, S., Søgaard, D.H., Cooper, M., Pucko, M., Lennert, K., Papakyriakou, T.N., Wang, F., Geilfus, N.X., Guld, R.N., Ehn, J., McGinnis, D.F., Attard, K., Sievers, J., Deming, J.W. and Barber, D.. 2013. Ikaite crystal distribution in winter sea ice and implications for CO2 system dynamics. The Cryosphere 7: 707718.Google Scholar
Sandven, S. (editor). 2012. Daily updated time series of Arctic sea ice area and extent derived from SSMI data provided by NERSC. Bergen: Nansen Environmental and Remote Sensing Cantre, Arctic ROOS Secretariat. URL: http://arctic-roos.org/observations/satellite-data/sea-ice/ice-area-and-extent-in-arctic (accessed 01 September 2012).Google Scholar
Steig, E.J., Schneider, D.P., Rutherford, S.D., Mann, M.E., Comiso, J.C. and Shindell, D.T.. 2009. Warming of the Antarctic ice-sheet surface since the 1957 International Geophysical Year. Nature 457: 459462.Google Scholar
Syed, K.A., Pang, S.-F., Zhang, Y., Zeng, G. and Zhang, Y.-H.. 2012. Micro-Raman observation on the HPO42 association structures in an individual dipotassium hydrogen phosphate (K2HPO4) droplet. The Journal of Physical Chemistry A 116: 15581564.CrossRefGoogle Scholar
Trevena, A.J., and Jones, G.B.. 2006. Dimethylsulphide and dimethylsulphoniopropionate in Antarctic sea ice and their release during sea ice melting. Marine Chemistry 98: 210222.Google Scholar
Trevena, A.J., Jones, G.B., Wright, S.W. and Van den Enden, R.L.. 2000. Profiles of DMSP, algal pigments, nutrients and salinity in pack ice from eastern Antarctica. Journal of Sea Research 43: 265273.Google Scholar