Ikaite precipitation in a lacustrine environment – implications for palaeoclimatic studies using carbonates from Laguna Potrok Aike (Patagonia, Argentina)

doi:10.1016/j.quascirev.2012.05.024

Quaternary Science Reviews

Volume 71, 1 July 2013, Pages 46-53

https://doi.org/10.1016/j.quascirev.2012.05.024 Get rights and content

Abstract

The monoclinic mineral ikaite (CaCO₃ · 6H₂O) and its pseudomorphs are potentially important archives for palaeoenvironmental reconstructions. Natural ikaite occurs in a small temperature range near freezing point and is reported mainly from marine and only rarely from continental aquatic environments. Ikaite transforms to more stable anhydrous forms of CaCO₃ after an increase in temperature or when exposed to atmospheric conditions. The knowledge about conditions for natural ikaite formation, its stable isotope fractionation factors and isotopic changes during transformation to calcite is very restricted. Here, for the first time, primary precipitation of idiomorphic ikaite and its calcite pseudomorphs are reported from a subsaline lake, Laguna Potrok Aike, in southern Argentina. The calculated stable oxygen isotope fractionation factor between lake water and ikaite-derived calcite (α_PAI = 1.0324 at a temperature of 4.1 °C) is close to but differs from that of primarily inorganically precipitated calcite. Pseudomorphs after ikaite rapidly disintegrate into calcite powder that is indistinguishable from μm-sized calcite crystals in the sediment record of Laguna Potrok Aike suggesting an ikaite origin of sedimentary calcites. Therefore, the Holocene carbonates of Laguna Potrok Aike have the potential to serve as a recorder of past hydrological variation.

Section snippets

Introduction and site description

Modern ikaite is a mineral frequently observed in certain marine anoxic sediments (e.g. Suess et al., 1982; Shearman and Smith, 1985; Stein and Smith, 1986; Jansen et al., 1987; Hacke et al., 1994; Schubert et al., 1997; Zabel and Schulz, 2001) and more currently also in Antarctic and Arctic sea ice (Dieckmann et al., 2008, 2010). To our knowledge, however, only four locations of modern occurrences of ikaite in fresh and brackish water systems have been reported. At all these locations ikaite

Material and methods

Lake water temperatures between March 2006 and October 2008 were recorded every 6 h by Minilog thermistors (M-08TR, Vemco ltd., Canada) in 0 and 90 m water depth attached to a mooring in the centre of the lake. Two sediment traps were also installed in 90 m water depth which had an active area of 55 cm² (Ohlendorf et al., 2013 for more details). pH, electric conductivity (EC), salinity, and the alkalinity were measured with an Universal Pocket Meter (Multi 340i, WTW). The water chemistry

Evidence for modern ikaite and its pseudomorphs

The single crystal X-ray structure analysis of an exemplary carbonate crystal precipitated on aquatic moss and stored cool after sampling gave evidence of the mineral ikaite (Table 1). The structure was solved and refined in the space group C2/c with Z = 4 and the lattice parameters a = 8.7906 (13) Å, b = 8.2850 (9) Å, c = 10.9890 (17) Å, and β = 110.589 (17) °. The calculated density at the temperature of 253 K is 1.846 g cm⁻³. The final structure refinement including hydrogen positions

Discussion

The occurrence of pseudomorphs after ikaite is usually interpreted as an indicator of cold-water temperatures (e.g., Greinert and Derkachev, 2004). Our results demonstrate that during transformation from ikaite to calcite no effect on the oxygen and only minor effects on the carbon isotopic composition occurred. Hence the calcite pseudomorphs recorded the carbonate isotopic composition of the original ikaite which is in accordance with Greinert and Derkachev (2004). Stable isotope analyses on

Conclusions

During the PASADO drilling campaign transparent carbonate crystals were collected in Laguna Potrok Aike and classified as the mineral ikaite. These crystals, their pseudomorphs and the microscopic carbonate crystals in the lake sediment were studied with mineralogical, electron microscopic and isotopic methods resulting in the following conclusions:

(1)
The lake water of Laguna Potrok Aike is supersaturated with respect to Ca-carbonates but the precipitation of anhydrous carbonates is inhibited by

Acknowledgements

We thank H. Wissel for the isotopic analysis of the lake water and E. Wessel for assistance with the SEM. This study was partially financed by the German Research Foundation (DFG MA 4235/4-1). This research would not have been possible without the fieldwork carried out in the framework of the "Potrok Aike Maar Lake Sediment Archive Drilling Project" (PASADO) supported by the International Continental Scientific Drilling Program (ICDP). Funding for PASADO was provided by the ICDP, the German

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Highly alkaline (pH 9–12) waters can arise from a range of globally significant and environmentally impactful industrial processes such as lime, steel and cement production, alumina refining and energy generation (e.g. combustion ashes). Such residue storage sites are often characterized by extreme geochemical conditions that can be hazardous to aquatic life but are quickly becoming a critical focus for resource recovery and carbon capture initiatives. The very high rates of mineral precipitation at these sites can give rise to the formation of transient minerals that are not currently well understood. As such our estimates of carbon budgets and understanding of trace metal dynamics at highly alkaline sites is currently limited. This study provides a significant advancement in the basis for characterising hyperalkaline carbonate systems through identification and chemical analysis of transient minerals forming in sites receiving high pH (>11) steel slag leachate in northern England. Whilst most of the secondary deposits at the study sites appear to be dominated by calcite, this study provides the first account of ikaite (CaCO₃.6H₂O) crystallization within steel-slag leachate, using novel field (Fourier Transform Infra-Red) supported by rapid laboratory (X-Ray Diffraction) validation. This study suggests that ikaite is a secondary mineral with a primary phase being amorphous calcium carbonate (ACC). Trace element analysis of ikaite forming in these steel-slag leachate affected waters is demonstrates its strong affinity to incorporate relatively large inventories of potentially harmful metals (e.g. lead and cadmium). Importantly, ikaite is only stable at low temperatures (−4 to 8 °C) and thus is of significant concern given its potential to release hazardous pulses of contamination during warming events in the spring. The findings provide an improved understanding of carbonate precipitation processes at highly alkaline sites which in turn should influence future research endeavours around mineral carbonation, trace metal dynamics and environmental remediation at these sites globally.
The mechanisms and stable isotope effects of transforming hydrated carbonate into calcite pseudomorphs
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Ikaite (CaCO₃·6H₂O) and monohydrocalcite (CaCO₃·H₂O; MHC) are hydrated carbonates that form at frigid (<9 °C) temperatures. During gradual heating and dehydration, the more thermodynamically stable anhydrous calcite replaces and pseudomorphs ikaite and MHC. Previously, ikaite pseudomorphs have been identified in the sedimentary record by characteristic replacive macro- and microtextures and interpreted as evidence for near-freezing marine paleotemperatures. Prior to this study, we lacked an understanding of isotopic exchange during mineral dehydration necessary to interpret isotopic compositions of such fabrics. Specifically, do the stable isotopic compositions of ikaite pseudomorphs preserve the primary environmental signal, or are they altered during mineral transformation? Through heating experiments of MHC from Ikka Fjord, we find that δ¹⁸O_CARB and Δ₄₇ decreased, while δ¹³C_CARB remained nearly unchanged during progressive dehydration. An oxygen isotopic exchange model fitted to experimental data suggests that the isotopic changes reflected partial re-equilibration of δ¹⁸O_CARB and Δ₄₇ towards the new diagenetic conditions due to oxygen equilibrium exchange between CO₃²⁻ and H₂O within the MHC lattice. However, this process never reaches full equilibrium, an effect we argue reflects the fact that structural H₂O escapes the solid carbonate structure faster than isotopic exchange can reach equilibrium. In addition, labelled water experiments demonstrated that oxygen isotopic exchange also occurs with secondary external waters during dehydration.
We apply this new framework to interpret the isotopic compositions of Pleistocene ikaite pseudomorphs from Mono Lake (CA, USA) high-stand deposits, which have undergone subaerial dehydration. Specifically, dehydration diagenetic overprinting of Δ₄₇ similar to the results of our controlled heating experiments can explain the warm temperatures, 6–26 °C, recorded by ikaite pseudomorphs and the higher δ¹⁸O_CARB recorded by ikaite pseudomorph compared to other Pleistocene Mono Lake calcite tufas. We show that Mono Lake ikaite pseudomorph tufa isotopic data can be explained in a model scenario where approximately coeval precursor ikaite and other calcite tufas in Pleistocene Mono Lake formed from similar fluid compositions but at different water temperatures, likely related to changing seasons. In summary, we show that the isotopic composition of ikaite and MHC pseudomorphs can be used for paleoclimate reconstruction of water temperature, δ¹⁸O_CARB, δ¹⁸O_fluid, and δ¹³C_CARB when considering dehydration diagenetic effects.
Glendonites throughout the Phanerozoic
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Ikaite is a metastable calcium carbonate hexahydrate (CaCO3·6H2O), which naturally occurs in environments characterized by temperatures of −2 to +7 °C. It is therefore considered as an indicator of cold water conditions, although its suitability as a paleotemperature indicator is still questioned, especially as under certain laboratory conditions, ikaite was formed at temperatures of up to 35 °C. At warmer temperatures, ikaite becomes unstable and quickly decomposes to anhydrous calcium carbonate(s) and water. However, the primary ikaite crystal morphology can occasionally be preserved as a pseudomorph, generally known as ‘glendonite’. Even in early studies, glendonites were considered as indicators of cold climates due to their association with cold water fauna, dropstones and other cold climate indictors. We are using a global glendonite database with more than 900 occurrences to reconstruct their distribution through Phanerozoic time. Based on these reconstructions we observe that the Early Paleozoic glendonites cannot be directly correlated with cooler global climate episodes, but are restricted to the upwelling of cold waters on the wide shelf of the Baltic paleobasin. Carboniferous–Permian occurrences correlate with the Late Paleozoic Ice Age, one of the longest and most prominent glacial events in Earth's history. Our plate reconstructions suggest that most Late Paleozoic glendonite occurrences are restricted to the high latitudes. Glendonites are absent from Triassic and Upper Cretaceous sediments around the world, which were deposited during periods generally considered as the hottest of the Phanerozoic. However, glendonites are numerous within certain Jurassic and Cretaceous strata deposited during well-known cooling intervals. Our reconstructions suggest that the majority of Mesozoic glendonite occurrences are confined to the polar or near-polar regions. Paleogene–Neogene occurrences are restricted to the middle and high latitudes of the northern hemisphere. In addition to glendonites from marine deposits, a few findings are known from continental environments. Quaternary ikaites and glendonites have a widespread distribution in marine settings close to polar seas (mainly Arctic shelves) or on deep-water continental margins (e.g., Zaire deep fan, Nankai Trough, Sakhalin Island slope), with rare findings in terrestrial environments such as lakes, ice sheets and caves. In contrast to Quaternary occurrences, the older Mesozoic and Paleozoic glendonites are confined to shallow marine shelf environments. This discrepancy is likely to be related to the lower preservation potential of deep-water and terrestrial sediments in deep time, as opposed to sediments deposited at high rates along the margins of epicontinental or marginal seas.
On the nucleation of ikaite (CaCO<inf>3</inf>x6H<inf>2</inf>O) – A comparative study in the presence and absence of mineral surfaces
2022, Chemical Geology
The formation of ikaite (CaCO₃x6H₂O) was studied in the presence and absence of quartz and mica surfaces using desupersaturation curves from cryo-mixed-batch-reactor experiments. Upon nucleation and growth within the reactor, the solution approached solubility of the precipitating carbonate phase. For ikaite, a solubility constant of log K_{sp ikaite} = −7.3 ± 0.1 was found (T = 0 °C). At supersaturations Ω_ikaite < 15, the nucleation of ikaite was significantly promoted by the presence of quartz or mica. This promotion prevented a competing nucleation of anhydrous calcium carbonates. In the presence of quartz or mica, therefore, ikaite forms over a much broader supersaturation range than in the absence. Similarly strong promotors of ikaite nucleation rather than anhydrous carbonate nucleation were previously attributed to calcite-inhibiting substances only.
At supersaturations Ω_ikaite ≥ 8, application of classical nucleation theory on induction periods of ikaite formation yielded an effective interfacial energy of 15 ± 3 mJ/m². Compared to data of anhydrous CaCO₃ phases, this interfacial energy is low and expresses the highly hydrated character of ikaite. At supersaturations Ω_ikaite ≥ 18, a transient amorphous phase appeared besides ikaite.
Our results show that a comprehensive understanding of ikaite formation in natural settings requires consideration not only of supersaturation and presence of calcite-inhibitors but also of the presence or absence of mineral surfaces capable of promoting heterogeneous nucleation of ikaite.
The minerals ikaite and its pseudomorph glendonite: Historical perspective and legacies of Douglas Shearman and Alec K. Smith
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Citation Excerpt :
Ikaite crystals retrieved from Potrok Aike, a caldera lake in Patagonia with hypersaline cool waters (4 °C), transformed quickly to calcite pseudomorphs (Oehlerich et al., 2009). The surrounding sediments are of volcanic origin, while the lake water is phosphorous-rich and alkaline (Oehlerich et al., 2013). In this lake, ikaite is often associated with aquatic macrophytes and cyanobacteria colonies, which may have a catalytic role, or may provide a protective film on the ikaite, as occurs in Ikka Fjord (Trampe et al., 2016).
This paper presents a historical perspective of the discovery of, and aspects of, glendonite and ikaite, through the legacy of British mineralogists Douglas Shearman and Alec K. Smith. Much of the knowledge, literature review and synthesis presented in the following paper raises from the original work and discussions that these two key figures in mineralogy shared with the geological community both in the form of their official communications but also as informal discussions with the first author. Through our extensive review, we show that, while the link between ikaite and glendonite is now undeniable, questions remain.
New multibeam mapping of the unique Ikaite columns in Ikka Fjord, SW Greenland
2022, Marine Geology
Ikka Fjord in SW Greenland is world famous for its submarine, cold-water craving ikaite (CaCO₃·6H₂O) tufa columns. Due to the uniqueness of the columns, Ikka Fjord is declared a protected area by the Greenlandic authorities. In the summers of 2018–19, multibeam sonar bathymetry and aerial drone photogrammetric surveys were made in Ikka Fjord mapping and counting the columns and comparing the results to data from geophysical surveys of the fjord in 1995–96. The new surveys provide highly detailed maps of the fjord bathymetry and its columns, their height and position, and several hitherto unknown pockmarks in the seabed. A total of 938 individual columns and structures ranging 0.5–20 m in height from the sea floor were identified: a number surpassing the 678 taller columns (> 1 m) known from previous mapping. Our results support previous observations that the columns are restricted to the spatial extents of the Grønnedal-Íka igneous complex. The new survey data show that column distribution exhibits lineations and variable density over the fjord floor, notably that the innermost central deep part is free of columns. The tallest columns are observed to grow up to the halocline at approximately 2–4 m water depth. The majority of columns have reached only 15–50% of their growth potential. The ~60 columns of maximum growth stand in clusters, interpreted as representing exceptionally favourable growth settings. New seawater data collected in 2019 shows a worrying increase in temperature since the previous measurements in 1995 and 2007–2009, which could potentially affect the stability of the delicate columns of Ikka Fjord.

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¹: Present address: Institute of Geography, University of Erlangen-Nürnberg, D-91054 Erlangen, Germany.

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Ikaite precipitation in a lacustrine environment – implications for palaeoclimatic studies using carbonates from Laguna Potrok Aike (Patagonia, Argentina)

Abstract

Section snippets

Introduction and site description

Material and methods

Evidence for modern ikaite and its pseudomorphs

Discussion

Conclusions

Acknowledgements

Environmental history of southern Patagonia unravelled by the seismic stratigraphy of Laguna Potrok Aike

Sedimentology

Kinetic of calcite nucleation: magnesium ion inhibition and ionic strength catalysis

Journal of Geophysical Research

The solubility and stabilization of ikaite CaCO3 * 6H2O from 0° to 25°C: environmental and paleoclimatic implications for thinolite tufa

Journal of Geology

Ikaite precipitation by mixing of shoreline springs and lake water, Mono Lake California, USA

Geochimica et Cosmochimica Acta

Seasonal dynamics of stable isotopes and element ratios in authigenic calcites during their precipitation and dissolution, Sacrower See (northeastern Germany)

Journal of Limnology

Submarine columns of ikaite tufa

Nature

Ikaite tufa towers in Ikka Fjord, southwest Greenland: their formation by mixing of seawater and alkaline spring water

Journal of Sedimentary Research

Comparison of stable isotope reference samples

Nature

Geochemistry of ikaite formation at Mono Lake, California – implications for the origin of tufa mounds

Geology

Glendonites as a paleoenvironmental tool: implications for early Cretaceous high latitude climates in Australia

Geochimica et Cosmochimica Acta

The crystal structure of calcium carbonate hexahydrate at ∼−120°

Inorganic Chemistry

Calcium carbonate as ikaite crystals in Antarctic sea ice

Geophysical Research Letters

Ikaite (CaCO3*6H2O) discovered in Arctic sea ice

The Cryosphere

On using carbon and oxygen isotope data from glendonites as paleoenvironmental proxies: a case study from the Permian system of eastern Australia

Journal of Sedimentary Research

Glendonites and methane-derived Mg-calcites in the Sea of Okhotsk, Eastern Siberia: implications of a venting-related ikaite/glendonite formation

Marine Geology

Climatically induced lake level changes during the last two millennia as reflected in sediments of Laguna Potrok Aike, southern Patagonia (Santa Cruz, Argentina)

Journal of Paleolimnology

Lateglacial and Holocene wet–dry cycles in southern Patagonia: chronology, sedimentology and geochemistry of a lacustrine record from Laguna Potrok Aike, Argentina

The Holocene

Pore water chemistry

Oxygen isotopes in meteoric calcite cements as indicators of continental paleoclimate

Geology

Refinement of the structure of ikaite, CaCO3 · 6H2O

Zeitschrift für Kristallographie

Inhibition of calcite crystal growth by inorganic phosphate

Journal of Colloid and Interface Science

The petrology of ikaite pseudomorphs and their diagenesis

Proceedings of the Geologists' Association

Ikaite from cold spring water at Shiowakka, Hokkaido, Japan

Journal of Mineralogy, Petrology and Geology

Factors controlling the transformation of natural ikaite from Shiowakka, Japan

Geochemical Journal

Ikaite pseudomorphs in the Zaire deep-sea fan: an intermediate between calcite and porous calcite

Geology

Southern hemispheric westerlies control the spatial distribution of modern sediments in Laguna Potrok Aike, Argentina

Journal of Paleolimnology

Equilibrium and nonequilibrium oxygen isotope effects in synthetic carbonates

Geochimica et Cosmochimica Acta

Lithology, radiocarbon dating and sedimentological interpretation of the 51 ka BP lacustrine record from Laguna Potrok Aike, southern Patagonia

Quaternary Science Reviews

Contribution of biogenic methane to ikaite formation in the Kara Sea; evidence from the stable carbon isotope geochemistry

Proceedings in Marine Science

Low-temperature thermodynamic model for the system Na2CO3–MgCO3–CaCO3–H2O – the solubility of a non-ideal gas

Geochimica et Cosmochimica Acta

The solubility and stabilization of ikaite CaCO₃ * 6H₂O from 0° to 25°C: environmental and paleoclimatic implications for thinolite tufa

Ikaite (CaCO₃*6H₂O) discovered in Arctic sea ice

Refinement of the structure of ikaite, CaCO₃ · 6H₂O

Low-temperature thermodynamic model for the system Na₂CO₃–MgCO₃–CaCO₃–H₂O – the solubility of a non-ideal gas