Research on Ikaite—Natural Occurrences and Synthetic Mineral Precipitation

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Crystallography and Physical Chemistry of Minerals & Nanominerals".

Deadline for manuscript submissions: closed (13 May 2023) | Viewed by 7414

Special Issue Editors


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Guest Editor
Institute of Earth Sciences, University of Iceland, 101 Reykjavík, Iceland
Interests: geochemistry; fluid-rock reactions; carbonates; ikaite; CO2 sequestration

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Guest Editor
Department of Geology, School of Natural Sciences, Trinity College Dublin, Dublin 2, Ireland
Interests: mineral formation; mineral-water interaction processes; carbonate mineralogy and geochemistry

Special Issue Information

Dear Colleagues,

This Special Issue of Minerals focuses on research on the mineral ikaite (CaCO3·6H2O), which despite being metastable is found at several localities around the world. Its formation is linked to aqueous environments, and it precipitates in the whole range of natural aqueous environments from marine to fresh water. Ikaite can precipitate close to the water surface, in sea ice, on the beach and deep within sediments. Oddities such as Greenlandic shrimps and industrial pipelines are other known sites for the growth of ikaite. In general, these localities are characterized by low temperature ranging from below zero to approximately +10 °C. At some localities, ikaite forms solely during the wintertime. Nevertheless, laboratory experiments have found ikaite to precipitate at 25 °C or even higher if certain inhibitors of calcite are present in solution. A great deal of research has focused on the phosphate-inhibiting effects on calcite in connection with ikaite formation, but recent research has shown that other inhibitors of calcite ± aragonite can lead to the precipitation of ikaite, such as the presence of Mg in marine systems. Researchers working on calcium carbonate phases in laboratory experiments often come across ikaite, especially when working at low temperatures as stated above. Because ikaite is a metastable mineral phase at all P-T conditions found on Earth, kinetics is at play when ikaite is forming (i.e., rather than thermodynamics). With this Special Issue, we would like to narrow down what geochemical and perhaps even biogeochemical factors control ikaite formation at localities where ikaite is found in Nature. We must be aware that ikaite might not be the first mineral phase to precipitate, but it could be amorphous calcium carbonate (ACC,) as seen from laboratory experiments. Therefore, it is crucial to add to this Special Issue what these experiments have taught us about the different calcium carbonate phases, and what controls ikaite to form either directly from solution or from ACC, and why ikaite when encountered is favored as a calcium carbonate phase over calcite, aragonite, vaterite, and/or monohydrocalcite(s). For what time intervals can we expect ikaite to remain stable, and what mineral alteration pathways can be expected? As already observed both in nature and in experiments, ikaite does not always transform directly into calcite, but takes other mineral pathways depending on, for example, the chemistry of the aqueous environment or solution, possible temperature or pH changes inflicted on the system, and the rate of these changes. The compiled knowledge of this Special Issue of Minerals will be of importance to anyone working on ikaite and research attempting to use the presence of ikaite or what are believed to be pseudomorphs of ikaite as paleoclimate indicators. A Special Issue on Ikaite is highly called for in order to provide an overview of the multiple factors that can lead to its formation, and what could preserve them to eventually allow them to form pseudomorphs composed of calcite or aragonite.

Dr. Gabrielle J. Stockmann
Dr. Juan Diego Rodríguez-Blanco
Guest Editors

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Keywords

  • natural occurrences of ikaite worldwide
  • synthetic ikaite mineral precipitation
  • (bio-)geochemical controls on ikaite formation
  • parameters favouring metastable minerals
  • hydrated and amorphous calcium carbonates
  • ikaite as a cold-climate paleo indicator

Published Papers (4 papers)

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Research

19 pages, 13420 KiB  
Article
Transgression Related Holocene Coastal Glendonites from Historic Sites
by Bo Schultz, Jennifer Huggett, Bas van de Schootbrugge, Clemens V. Ullmann and Mathias C. Broch
Minerals 2023, 13(9), 1159; https://doi.org/10.3390/min13091159 - 31 Aug 2023
Viewed by 1135
Abstract
This study examines the occurrence of glendonite along coastlines since 1825, which have been previously referred to under different names such as Pseudogaylussite, Fundylite, and Kool Hoot across eleven sites. By utilising element ratios and 14C radiometric dating techniques, we establish a [...] Read more.
This study examines the occurrence of glendonite along coastlines since 1825, which have been previously referred to under different names such as Pseudogaylussite, Fundylite, and Kool Hoot across eleven sites. By utilising element ratios and 14C radiometric dating techniques, we establish a more accurate chronology for these varied sites ranging from 10 to 1 thousand years before the present (Ky BP). Sites include tidal flats, coastal barrier islands, and Wadden Sea environments. While some sites still exist, others are only known through publications and museum collections. Our research expands upon previous findings by presenting petrographic evidence that correlates with glendonite formation. Through the examination of the Olenitsa site on the Kola Peninsula, we demonstrate that marine bioclasts enclosed within concretions surrounding glendonites provide temporal context, suggesting that these outcrops were formed during a single event under changing conditions. Notably, certain sediment structures at selected sites indicate the occurrence of cold-water ice-raft storm events and the presence of drop stones. Furthermore, our paper explores the association of historic coastal sites with the formation of ikaite, highlighting the limitations of relying solely on geochemistry and isotopic analysis for interpretation. Intriguingly, we observe that pseudomorphs are abundant in specific areas but absent in adjacent regions with similar environmental, physical, and chemical conditions. No apparent connection is found between volcanic dust cloud-induced cold spells and glendonite. The distribution of coastal glendonites is more likely related to periods of climatic cooling through other means. We show that radiometric dating with 14C provides an indication of age, but the results can be erroneous due to the inclusion of older carbon sources in the analysis. The oldest locations discussed in this study are Kool Hoot (Alaska) and the river Clyde (Scotland), and the youngest glendonites discussed are from the Bay of Fundy in Canada. Occurrences from the Wadden Sea are intermediate in age and sit between the other two groups. The age of the Olenitsa site on the Russian Kola Peninsula is uncertain and still debated. We show that measuring the ratio of Mg/Ca can indicate how much the recrystallised ikaite preserved as calcite is influenced by diagenetic pore waters. Full article
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13 pages, 21616 KiB  
Article
Links between Ikaite Morphology, Recrystallised Ikaite Petrography and Glendonite Pseudomorphs Determined from Polar and Deep-Sea Ikaite
by Bo Pagh Schultz, Jennifer Huggett, Clemens V. Ullmann, Heidemarie Kassens and Martin Kölling
Minerals 2023, 13(7), 841; https://doi.org/10.3390/min13070841 - 22 Jun 2023
Cited by 3 | Viewed by 1398
Abstract
Petrography of recrystallised ikaite from Ocean Drilling Program material has been presented previously from Nankai Trough and Congo (ex-Zaire) deep-sea fan. This paper expands on the Nankai Trough ikaite observations, drawing on evidence from Laptev Sea, South Georgia, Okhotsk Sea, and coastal lagoon [...] Read more.
Petrography of recrystallised ikaite from Ocean Drilling Program material has been presented previously from Nankai Trough and Congo (ex-Zaire) deep-sea fan. This paper expands on the Nankai Trough ikaite observations, drawing on evidence from Laptev Sea, South Georgia, Okhotsk Sea, and coastal lagoon Point Barrow. However, even though many ikaite and glendonite sites occur at high latitudes, it cannot be that ikaite forms exclusively in polar environments, as demonstrated by the occurrences in the low latitude low temperature deep sea sediments offshore Gulf of Guinea (Angola Congo) and mid-latitude deep-sea trenches offshore Japan. Recrystallised ikaite occurs as mm large, zoned calcite crystals in all samples, along with secondary phases of calcite. Our data set is unique in that the origin, storage, and recrystallisation process of natural formed ikaite is recorded in detail and confirms that glendonite petrographic characteristics are a consequence of the structure and chemistry of recrystallising ikaite and not the physical or geochemical environment. The transformation of man-made ikaite to calcite as recorded in laboratory studies, is a process very similar to the one we have observed for natural ikaite. Most significant is that there is variation in the order of the calcite types within a single sample, leading to the conclusion that the variation is a consequence of impurities and geochemical variability in the ikaite, not the external environment. Morphological observations reveal similarities in ikaite and glendonite, this and the similarity in internal textures in glendonite and recrystallised ikaite confirms that glendonite may be used as an indicator of past presence of ikaite. Full article
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29 pages, 4216 KiB  
Article
Calcium Carbonate Hexahydrate (Ikaite): History of Mineral Formation as Recorded by Stable Isotopes
by Michael J. Whiticar, Erwin Suess, Gerold Wefer and Peter J. Müller
Minerals 2022, 12(12), 1627; https://doi.org/10.3390/min12121627 - 17 Dec 2022
Cited by 5 | Viewed by 1990
Abstract
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 [...] Read more.
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. Full article
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20 pages, 7307 KiB  
Article
Mineral Changes to the Tufa Columns of Ikka Fjord, SW Greenland
by Gabrielle J. Stockmann, Paul Seaman, Tonci Balic-Zunic, Mark Peternell, Erik Sturkell, Bengt Liljebladh and Richard Gyllencreutz
Minerals 2022, 12(11), 1430; https://doi.org/10.3390/min12111430 - 10 Nov 2022
Cited by 5 | Viewed by 1699
Abstract
The submarine tufa columns of Ikka Fjord in Southwest Greenland have been studied during multiple field campaigns since 1995. The fjord contains close to thousand columns previously shown to consist of the metastable carbonate mineral ikaite (CaCO3·6H2O), which requires [...] Read more.
The submarine tufa columns of Ikka Fjord in Southwest Greenland have been studied during multiple field campaigns since 1995. The fjord contains close to thousand columns previously shown to consist of the metastable carbonate mineral ikaite (CaCO3·6H2O), which requires near-freezing conditions to remain stable over longer periods of time. During a field campaign to Ikka Fjord in the summer of 2019, seawater temperatures of 6–9 °C and visual physical changes to the columns were observed. These are the highest recorded seawater temperatures measured in Ikka Fjord in over three decades of research. In response, three selected columns at three different locations were sampled at their bases, middle, and top sections for mineralogical analysis. These samples were supplemented by a four further column samples and an extensive hydrographical campaign during fieldwork in the summer 2021. Here, we report the results of the mineralogical analyses performed by X-ray diffraction and µ-Raman Spectroscopy on these column samples. The results show that the columns analysed now consist of the less hydrated carbonate minerals, monohydrocalcite (CaCO3·H2O), aragonite, and calcite (CaCO3). One of the columns has completely altered into monohydrocalcite, whereas the other columns have crusts of ikaite and cores of monohydrocalcite ± aragonite and calcite. This change is interpreted as a dehydration reaction and mineral alteration from ikaite to monohydrocalcite continuing to aragonite ± calcite in response to being bathed in warming seawater. Hydrographic profilers and static dataloggers recorded seawater temperatures of 4–8 °C in the column-containing fjord areas during June–August 2021. The upper parts of the columns are particularly exposed to temperatures > 6 °C, considered to be the long-term stability threshold of ikaite in Ikka Fjord. The mineral dehydration reactions are irreversible. It is therefore predicted in a warming Arctic, ikaite will only appear as new growth on the columns for a short period, and that with time, the columns of Ikka Fjord will change mineralogy into mainly monohydrocalcite. Full article
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