Hostname: page-component-848d4c4894-tn8tq Total loading time: 0 Render date: 2024-06-21T11:50:41.007Z Has data issue: false hasContentIssue false

Chemical controls on ikaite formation

Published online by Cambridge University Press:  29 May 2018

Elin Tollefsen*
Affiliation:
Department of Geological Sciences, Stockholm University, 106 91 Stockholm, Sweden
Gabrielle Stockmann
Affiliation:
Department of Geological Sciences, Stockholm University, 106 91 Stockholm, Sweden
Alasdair Skelton
Affiliation:
Department of Geological Sciences, Stockholm University, 106 91 Stockholm, Sweden
Carl-Magnus Mörth
Affiliation:
Department of Geological Sciences, Stockholm University, 106 91 Stockholm, Sweden
Christophe Dupraz
Affiliation:
Department of Geological Sciences, Stockholm University, 106 91 Stockholm, Sweden
Erik Sturkell
Affiliation:
Department of Earth Sciences, University of Gothenburg, 405 30 Gothenburg, Sweden

Abstract

The hydrated carbonate mineral ikaite (CaCO3·6H2O) is thermodynamically unstable at all known conditions on Earth. Regardless, ikaite has been found in marine sediments, as tufa columns and in sea ice. The reason for these occurrences remains unknown. However, cold temperatures (<6°C), high pH and the presence of Mg2+ and SO42– in these settings have been suggested as factors that promote ikaite formation. Here we show that Mg concentration and pH are primary controls of ikaite precipitation at 5°C. In our experiments a sodium carbonate solution was mixed with seawater at a temperature of 5°C and at a constant rate. To test the effect of Mg2+ and SO42– we used synthetic seawater which allowed us to remove these elements from the seawater. The pH was controlled by different ratios of Na2CO3 and NaHCO3 in the carbonate solution. We found that ikaite precipitated when both seawater and synthetic seawater from which SO4 had been removed were used in the experiments. However, ikaite did not precipitate in experiments conducted with synthetic seawater from which Mg had been removed. In these experiments, calcite precipitated instead of ikaite. By varying the Mg concentration of the synthetic seawater and the pH of the sodium carbonate solution, we constructed a kinetic stability diagram for ikaite and calcite as a function of Mg concentration and pH. One possible explanation of our finding is that Mg2+ inhibits calcite nucleation and thereby allows metastable ikaite to form instead.

Type
Article
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2018 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Footnotes

Associate Editor: Juraj Majzlan

References

Berner, R.A. (1975). The role of magnesium in the crystal growth of calcite and aragonite from sea water. Geochimica et Cosmochimica Acta, 39(4), 489504.Google Scholar
Bischoff, J.L., Fitzpatrick, J.A. and Rosenbauer, R.J. (1993 a) The solubility and stabilization of ikaite (CaCO3·6H2O) from 0° to 25°C: Environmental and paleoclimatic implications for Thinolite Tufa. Journal of Geology, 101, 2133.Google Scholar
Bischoff, J.L., Stine, S., Rosenbauer, R.J., Fitzpatrick, J.A. and Stafford, T.W. Jr. (1993 b) Ikaite precipitation by mixing of shoreline springs and lake water, Mono Lake, California, USA. Geochimica et Cosmochimica Acta, 57, 38553865.Google Scholar
Bots, P., Benning, L.G., Rodriguez-Blanco, J.D., Roncal-Herrero, T. and Shaw, S. (2012) Mechanistic insights into the crystallization of amorphous calcium carbonate (ACC). Crystal Growth & Design, 12, 38063814, https://doi.org/10.1021/CG300676bGoogle Scholar
Buchardt, B., Israelson, C., Seaman, P. and Stockmann, G. (2001) Ikaite tufa in Ikka Fjord, southwest Greenland: Their formation by mixing of seawater and alkaline spring water. Journal of Sedimentary Research, 71, 176189.Google Scholar
Burton, E.S. and Walter, L.M. (1986) The effect of orthophosphate on carbonate mineral dissolution rates in seawater. Chemical Geology, 56, 313323.Google Scholar
Council, T.C. and Bennett, P.C. (1993) Geochemistry of ikaite formation at Mono Lake, California: implications for the origin of tufa mounds. Geology, 21, 971974.Google Scholar
Dahl, K. and Buchardt, B. (2006) Monohydrocalcite in the Arctic Ikka Fjord, SW Greenland: First Reported Marine Occurrence. Journal of Sedimentary Research, 76, 460471.Google Scholar
Davis, K.J., Dove, P.M. and De Yoreo, J.J. (2000) The role of Mg2+ as an impurity in calcite growth. Science, 290(5494), 11341137.Google Scholar
Degen, T., Sadki, M., Bron, E., König, U. and Nénert, G. (2014). Powder Diffraction 29(S2), S13S18.Google Scholar
Deleuze, M. and Brantley, S. (1997) Inhibition of calcite crystal growth by Mg2+ at 100°C and 100 bars: Influence of growth regime. Geochimica et Cosmochimica Acta, 7, 14751485.Google Scholar
Emeleus, C.H. (1964) The Grønnedal–Ika alkaline complex, South Greenland. Meddelelser om Grønland, 186, 75 pp.Google Scholar
Geilfus, N.X., Carnat, G., Dieckmann, G.S., Halden, N., Nehrke, G., Papakyriakou, T. 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(1), 244255, https://doi.org/10.1029/2012JC007980Google Scholar
Hansen, M.O., Buchardt, B., Kuhl, M. and Elberling, B. (2011) The fate of the submarine ikaite tufa columns in Southwest Greenland under changing climate conditions. Journal of Sedimentary Research, 81, 553561, https://doi.org/10.2110/jsr.2011.50Google Scholar
Hu, Y.B., Wolf-Gladrow, D.A., Dieckmann, G.S., Völker, C. and Nehrke, G. (2014) A laboratory study of ikaite (CaCO3· 6H2O) precipitation as a function of pH, salinity, temperature and phosphate concentration. Marine Chemistry, 162, 1018.Google Scholar
Huggett, J.M., Schultz, B.P., Shearman, D.J and Smith, A.J (2005) The petrology of ikaite pseudomorphs and their diagenesis. Proceedings of the Geologists' Association, 116, 207220.Google Scholar
Johnston, J., Merwin, H.E. and Williamson, E.D. (1916) The several forms of calcium carbonate. American Journal of Science, fourth series, 41, 473493.Google Scholar
Lennie, A.R. (2005) Ikaite (CaCO3·6H2O) compressibility at high water pressure: a synchrotron X-ray diffraction study. Mineralogical Magazine, 69(3), 325335.Google Scholar
Marland, G. (1975) The stability of CaCO3·6H2O (ikaite). Geochimica et Cosmochimica Acta, 39, 8391.Google Scholar
Meyer, H.J. (1984) The influence of impurities on the growth rate of calcite. Journal of Crystal Growth, 66(3), 639646.Google Scholar
Mucci, A., Canuel, R. and Zhong, S. (1989) The solubility of calcite and aragonite in sulfate-free seawater and the seeded growth kinetics and composition of the precipitates at 25°C. Chemical Geology, 74, 309320.Google Scholar
Nielsen, M.R., Sand, K.K., Rodriguez-Blanco, J.D., Bovet, N., Generosi, J., Dalby, K.N. and Stipp, S.L.S. (2016) Inhibition of calcite growth: combined effects of Mg2+ and SO42–. Crystal Growth & Design, 16, 61996207, https://doi.org/10.1021/acs.cgd.6b00536Google Scholar
Parkhurst, D.L. and Appelo, C.A.J. (2013) Description of Input and Examples for PHREEQC Version 3 – A Computer Program for Speciation, Batch-reaction, One-dimensional Transport, and Inverse Geochemical Calculations. U.S. Geological Survey Techniques and Methods, Book 6, Chapter A43, 497 pp. Available at https://pubs.usgs.gov/tm/06/a43/Google Scholar
Pauly, H. (1963) “Ikaite”, a new mineral from Greenland. Arctic, 16, 263264.Google Scholar
Pelouze, J. (1831) Sur la production artificielle du carbonate de chaux cristallise, et sur deux combinaisons de ce sel avec l'eau. Annales de Chimie et de Physique, ser. 2, 48, 301307.Google Scholar
Plummer, L.N. and Busenberg, E. (1982) The solubilities of calcite, aragonite and vaterite in CO2–H2O solutions between 0 and 90°C, and an evaluation of the aqueous model for the system CaCO3–CO2–H2O. Geochimica et Cosmochimica Acta, 46, 10111040.Google Scholar
Purgstaller, B., Dietzel, M., Baldermann, A. and Mavromatis, V. (2017) Control of temperature and aqueous Mg2+/Ca2+ ratio on the (trans-)formation of ikaite. Geochimica et Cosmochimica Acta, 217, 128143.Google Scholar
Rodriguez-Blanco, J.D., Shaw, S., Bots, P., Roncal-Herrero, T. and Benning, L.G. (2014) The role of Mg in the crystallization of monohydrocalcite. Geochimica et Cosmochimica Acta, 127, 204220.Google Scholar
Rodriguez-Ruiz, I., Veesler, S., Gómez-Morales, J., Delgado-López, J.-M., Grauby, O., Hammadi, Z., Candoni, N. and García-Ruiz, J.M. (2014) Transient calcium carbonate hexahydrate (ikaite) nucleated and stabilized in confined nano- and picovolumes. Crystal Growth, 14, 792802.Google Scholar
Schubert, C.J., Nürnberg, D., Scheele, N., Pauer, F. and Kriews, M. (1997) 13C isotope depletion in ikaite crystals: evidence for methane release from the Siberian shelves? Geo-Marine Letters, 17, 169174.Google Scholar
Stockmann, G., Tollefsen, E., Skelton, A., Brüchert, V., Balic-Zunic, T., Langhof, J., Skogby, H. and Karlsson, A. (2018) Control of a calcite inhibitor (phosphate) and temperature on ikaite precipitation in Ikka Fjord, southwest Greenland. Applied Geochemistry, 89, 1122.Google Scholar
Stumm, W. and Morgan, J.J. (1996) Aquatic Chemistry. Chemical Equilibria and Rates in Natural Waters. Third Edition. John Wiley & Sons, Inc., New York, 1022 pp.Google Scholar
Suess, E., Balzer, W., Hesse, K. F., Muller, P. J., Ungerer, C. A. and Wefer, G. (1982) Calcium carbonate hexahydrate from organic-rich sediments of the antarctic shelf: precursors of glendonites. Science, 216(4550), 11281131, https://doi.org/10.1126/science.216.4550.1128Google Scholar
Teichert, B.M.A. and Luppold, F.W. (2013) Glendonites from an Early Jurassic methane seep –Climate or methane indicators? Palaeogeography, Palaeoclimatology, Palaeoecology, 390, 8193, https://doi.org/10.1016/j.palaeo.2013.03.001Google Scholar
Toby, B.H. (2006) R factors in Rietveld analysis: How good is good enough? Powder diffraction, 21(01), 6770.Google Scholar
Trampe, E.C.L., Larsen, J.E.N., Glaring, M.A., Stougaard, P. and Kühl, M. (2016) In situ dynamics of O2, pH, light, and photosynthesis in ikaite tufa columns (Ikka Fjord,Greenland) – A unique microbial habitat. Frontiers in microbiology, 7, https://doi.org/10.3389/fmicb.2016.00722Google Scholar
Supplementary material: File

Tollefsen et al. supplementary material

Tollefsen et al. supplementary material 1

Download Tollefsen et al. supplementary material(File)
File 21.5 KB