Glendonite occurrences in the Tremadocian of Baltica: first Early Palaeozoic evidence of massive ikaite precipitation at temperate latitudes

Popov, Leonid E.; Álvaro, J. Javier; Holmer, Lars E.; Bauert, Heikki; Pour, Mansoureh Ghobadi; Dronov, A. V.; Lehnert, Oliver; Hints, Olle; Männik, Peep; Zhang, Zhiliang; Zhang, Zhiliang

doi:10.1038/s41598-019-43707-4

Cited by 21 publications

(10 citation statements)

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“…A possible scenario could be that ikaite precipitation lowers the pH in the parent solution beyond the limit for metastable nucleation of ikaite and thereafter the mineral starts to transform and is replaced by calcite pseudomorphically. Calcite has been reported as the primary replacement mineral in naturally occurring pseudomorphs (glendonite) after ikaite 11,24,36,46 . Our experiments confirm this common observation.…”

Section: Discussionmentioning

confidence: 99%

“…The results from these experiments may suggest that ikaite nucleation can also occur at temperature >7 °C in the natural environment. A recent study by Popov et al (2019) of fossil records in glendonite bearing strata suggested that ikaite nucleation probably occurred at water temperature >40 °C 36 . These findings call into question the use of ikaite as a paleotemperature indicator.…”

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Ikaite nucleation at 35 °C challenges the use of glendonite as a paleotemperature indicator

Tollefsen

Balić-Žunić

Mörth

et al. 2020

Sci Rep

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Glendonites have been found worldwide in marine sediments from the neoproterozoic era to the Quaternary period. the precursor of glendonite, ikaite (caco 3 • 6H 2 o), 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. Calcium carbonate, one of the most common naturally occurring minerals, has an important role in the global carbon cycle. Calcite is the stable form of calcium carbonate at the Earth's surface. However, growth of calcite is often inhibited by a range of external factors 1-3. This explains why metastable hydrous and anhydrous carbonate minerals tend to form instead of calcite. A common example is the precipitation of aragonite instead of calcite in the oceans. The Mg/Ca ratio of the seawater controls this precipitation: when this ratio exceeds 2, aragonite is favoured because Mg acts as an inhibitor of calcite growth 1,4. Two hydrous forms of calcium carbonate occur instead of calcite under certain conditions: monohydrocalcite (CaCO 3 •H 2 O) and ikaite (CaCO 3 •6H 2 O). Monohydrocalcite (MHC) has been found as calcareous incrustations and the main form of calcium carbonate in Lake Issyk-Kul, Republic of Kyrgyzstan 5 and as beach rocks around two salt lakes 6. Experimental results and investigation of natural samples indicate that the formation of MHC requires high Mg/Ca ratios and a pH >8 in the solution from which it forms 6-8. The second hydrous form, ikaite, is more common than MHC despite the narrow temperature range of its stability. The mineral was first discovered as tufa columns in Ikka Fjord, SW Greenland 9,10. Ikaite has only been observed in nature at temperatures between −2 and 7 °C 11. At temperatures >7 °C, ikaite transforms to calcite and water pseudomorphically or by decomposition. In spite of the narrow temperature range of its stability, ikaite has been widely reported: in organic rich marine sediments 12-14 , in sea ice 15,16 , in speleothems 17 , as seasonal tufa columns in alkaline lakes 18 , as precipitates in sediments or on the shores of alkaline springs or lakes 19,20 , and as precipitates in riverbeds caused by anthropogenic pollution 21. In 1982, Suess et al. discovered authigenic ikaite crystals in marine sediments, and the resemblance of these crystals to the pseudomorph glend...

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Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

Ikaite nucleation at 35 °C challenges the use of glendonite as a paleotemperature indicator

Tollefsen

Balić-Žunić

Mörth

et al. 2020

Sci Rep

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“…There is a notable absence of glendonite occurrences for a prolonged period of time below the Carboniferous, spanning the Devonian, Silurian, and Middle-Upper Ordovician. Lower Ordovician glendonites have only recently been discovered and described (Popov et al, 2019;Mikhailova et al, 2019), as until recently, they were known as a kind of "anthraconite" and were not considered to be glendonites. Their findings are restricted to Baltoscandia.…”

Section: Glendonite Distribution In Space and Timementioning

confidence: 99%

Database of global glendonite and ikaite records throughout the Phanerozoic

Rogov

Ershova

Vereshchagin

et al. 2021

Earth Syst. Sci. Data

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Abstract. This database of Phanerozoic occurrences and isotopic characteristics of metastable cold-water calcium carbonate hexahydrate (ikaite; CaCO3⚫6H2O) and their associated carbonate pseudomorphs (glendonites) has been compiled from academic publications, explanatory notes, and reports. Our database including more than 700 occurrences reveals that glendonites characterize cold-water environments, although their distribution is highly irregular in space and time. A significant body of evidence suggests that glendonite occurrences are restricted mainly to cold-water settings; however they do not occur during every glaciation or cooling event of the Phanerozoic. While Quaternary glendonites and ikaites have been described from all major ocean basins, older occurrences have a patchy distribution, which may suggest poor preservation potential of both carbonate concretions and older sediments. The data file described in this paper is available on Zenodo at https://doi.org/10.5281/zenodo.4386335 (Rogov et al., 2020).

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“…There is a notable absence of glendonite occurrences for a prolonged period of time below the Carboniferous, spanning the Devonian, Silurian and Middle−Upper Ordovician. Lower Ordovician glendonites have only recently been discovered and described (Popov et al, 2019;Mikhailova et al, 2019), as until recently, they were known as a kind of 'anthraconite' and were not considered as glendonites. Their findings are restricted to Baltoscandia.…”

Section: Database Contentsmentioning

confidence: 99%

Database of global glendonite and ikaite records throughout the Phanerozoic

Rogov¹,

Ershova²,

Vereshchagin³

et al. 2020

Preprint

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Abstract. This database of Phanerozoic occurrences and isotopic characteristics of metastable cold-water calcium carbonate hexahydrate (ikaite; CaCO3·6H2O) and their associated carbonate pseudomorphs (glendonites) has been compiled from academic publications and open-access reports. Our database including 690 occurrences reveals that glendonites characterize cold-water environments, although their distribution is highly irregular in space and time. A significant body of evidence suggests that glendonite occurrences are restricted mainly to cold-water settings, however they do not occur during every glaciation or cooling event of the Phanerozoic. While Quaternary glendonites and ikaites have been described from all major ocean basins, older occurrences have a patchy distribution, which may suggest poor preservation potential of both carbonate concretions and older sediments. The data file described in this paper is available on Zenodo at https://doi.org/10.5281/zenodo.3991964 (Rogov et al., 2020).

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Glendonite occurrences in the Tremadocian of Baltica: first Early Palaeozoic evidence of massive ikaite precipitation at temperate latitudes

Cited by 21 publications

References 54 publications

Ikaite nucleation at 35 °C challenges the use of glendonite as a paleotemperature indicator

Ikaite nucleation at 35 °C challenges the use of glendonite as a paleotemperature indicator

Database of global glendonite and ikaite records throughout the Phanerozoic

Database of global glendonite and ikaite records throughout the Phanerozoic

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