The mineral ikaite (CaCO3 center dot 6H(2)O) precipitates from a mixture of spring water and seawater as tufa columns which grow at a rate of up to 50 cm per year reaching heights of up to 18 m in Ikka Fjord, SW Greenland. In the fjord, column formation occurs only at the base of a nepheline syenite-carbonatite complex that flanks the fjord and an association has therefore been proposed. The spring water that seeps up at the bottom of the fjord is oversaturated in Na+ and HCO3-. In this study, we show that these ions were acquired by alteration reactions in the syenite-carbonatite complex: Na+ is released during replacement of nepheline by illite and analcime in nepheline-syenite rocks and HCO3- is released by oxidation of siderite to goethite in carbonatite rocks. The chemically charged groundwater mixes with seawater and gives rise to the formation of the tufa columns. We performed a mass balance to show that the mass of the carbonatite in the complex is more than sufficient to provide the CO2 needed to produce the observed mass of tufa columns. We estimated a time frame of similar to 600 years to produce the necessary CO2 to form the 700 ikaite columns in the fjord.

Ikaite (CaCO3 center dot 6H(2)O) forms submarine tufa columns in Ikka Fjord, SW Greenland. This unique occurrence is thought to relate to aqueous phosphate concentration and low water temperatures (< 6 degrees C). Phosphate ions are well-known inhibitors of calcite precipitation and Ikka Fjord has a naturally high-phosphate groundwater system that when mixing with seawater leads to the precipitation of ikaite. In the study presented here, experiments simulating conditions of Ikka Fjord show that a) the formation of ikaite is unrelated to the aqueous phosphate concentration (0-263 mu mol/ kg PO43-) in 0.1 M NaHCO3/0.1 M Na2CO3 solutions mixing with seawater at 5 degrees C and pH 9.6-10.6, and b) ikaite forms at temperatures up to 15 degrees C without phosphate and in open beakers exposed to air. Instead, supersaturation of ikaite and the seawater composition are the likely factors causing ikaite to precipitate in Ikka Fjord. This study shows that adding Mg2+ to a NaHCO3/Na2CO3 - CaCl2 mixed solution leads to the formation of ikaite along with hydrated Mg carbonates, which points to the high Mg2+ concentration of seawater, another known inhibitor of calcite, as a key factor promoting ikaite formation. In experiments at 10 and 15 degrees C, increasing amounts of either nesquehonite (Mg(HCO3)(OH)center dot 2H(2)O) or an amorphous phase co-precipitate with ikaite. At 20 degrees C, only the amorphous phase is formed. In warming Arctic seawater, this suggests Mg carbonate precipitation could become dominant over ikaite in the future.

The hydrated carbonate mineral ikaite (CaCO3 center dot 6H(2)O) 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 degrees 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 degrees C. In our experiments a sodium carbonate solution was mixed with seawater at a temperature of 5 degrees 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.

Glendonites have been found worldwide in marine sediments from the Neoproterozoic Era to the Quaternary Period. The precursor of glendonite, ikaite (CaCO3 · 6H2O), is metastable and has only been observed in nature at temperatures <7 °C. Therefore, glendonites in the sedimentary record are commonly used as paleotemperature indicators. However, several laboratory experiments have shown that the mineral can nucleate at temperatures>7 °C. Here we investigate the nucleation range for ikaite as a function of temperature and pH. We found that ikaite precipitated at temperatures of at least 35 °C at pH 9.3 −10.3 from a mixture of natural seawater and sodium carbonate rich solution. At pH 9.3, we observed pseudomorphic replacement of ikaite by porous calcite during the duration of the experiment (c. 5 hours). These results imply that ikaite can form at relatively high temperatures but will then be rapidly replaced by a calcite pseudomorph. This finding challenges the use of glendonites as paleotemperature indicators.