Calcium Carbonate Hexahydrate (Ikaite): History of Mineral Formation as Recorded by Stable Isotopes

• Published in: Minerals (Basel) Vol. 12; no. 12; p. 1627
• Main Authors: Whiticar, Michael J., Suess, Erwin, Wefer, Gerold, Müller, Peter J.
• Format: Journal Article
• Language: English
• Published: Basel MDPI AG 01.12.2022
• Subjects: Acidification; Alkalinity; Amino acids; Aspartic acid; Bransfield Strait; Calcite; Calcium; Calcium carbonate; calcium carbonate hexahydrate; Calcium carbonates; Carbon; Carbon dioxide; Carbon isotope ratio; Carbon isotopes; Carbonate minerals; Carbonates; Chromatography; Cold water; Crystal growth; Crystals; Decomposition; Diagenesis; Dissolved gases; Fluids; Fractionation; Gases; glendonite; Glutamic acid; High pressure; Hydration; Hydrocarbons; Hydrogen; ikaite; Isotope fractionation; Isotope ratios; Isotopes; Low temperature; Metabolism; Methanogenesis; Microorganisms; Minerals; Nucleation; Ocean floor; Organic compounds; Organic matter; Oxygen; Oxygen isotopes; Phosphates; Polar environments; Pore water; Ratios; Recrystallization; Sediments; stable isotope; Stable isotopes; Sulfate reduction; Sulfates; Sulphate reduction; Supersaturation; Van Arkel process; Water temperature; Zonal distribution; Arctic region; Greenland; Bransfield Strait
• ISSN: 2075-163X; 2075-163X
• DOI: 10.3390/min12121627

Calcium carbonate hexahydrate (ikaite) is a rare mineral that forms as metastable species in the organic-carbon-rich sediments of the King George Basin, Bransfield Strait, Antarctica, as a consequence of early diagenetic decomposition of organic matter under cold water (−1.4 °C) and high pressure (200 bar) conditions. Large crystals grow in the sediment immediately below the diagenetic transition between microbial sulfate reduction and methanogenesis at ~320 cm below sea floor (bsf). This process is reflected in the dissolved sulfate, total carbon dioxide, and methane concentrations, as well as in the carbon, hydrogen, and oxygen isotope chemistries of the interstitial fluids and dissolved gases of the host sediment. The ikaite crystal faithfully records in its zonal structure the changing carbon isotope ratio of the total dissolved carbon dioxide pool as it gradually diminishes during methanogenesis (δ13Cikaite = −17.5 to −21.4‰). These changes in the crystal’s host environment follow general Rayleigh carbon isotope fractionation. The oxygen isotopes of the ikaite carbonate (δ18Oikaite = 1.46 to 4.45‰) also show a strong zonal distribution, unrelated to temperature of formation, but perhaps controlled by the degree of recrystallization of ikaite to calcite. The crystal water of the ikaite is depleted 11‰ in 2H/1H (VSMOW) relative to the coexisting interstitial water, which is in excellent agreement with the isotope fractionation of other hydrated minerals. In addition to the in situ temperature and pressure, nucleation of the ikaite crystals in the Bransfield Basin sediments may be induced by the high alkalinity, high phosphate concentrations, and dissolved organic compounds. Intense microbial metabolism generates such compounds; of these, aspartic acid and glutamic acid may play an important role, as they do in biological and extracellular carbonate mineral precipitation. All indications are that low temperatures (such as of polar environments), high calcium carbonate supersaturation caused by interstitial methanogenesis, and a sufficiently large supply of dissolved phosphate and amino acids favor metastable ikaite formation. These conditions, modified by recrystallization, may be preserved in calcite glendonites, thinolites, and other calcitic pseudomorphs derived from ikaite and found throughout the ancient sedimentary record.