Abstract
Carbonate minerals are major contributors to carbon sequestration in geological deposits; however, their nature and behavior remain unclear. Amorphous magnesium carbonate (AMC) is formed as a precursor to crystalline magnesium carbonates and as a product of thermal decomposition of nesquehonite (NSQ). In this study, the AMCs formed during the crystallization and decomposition of NSQ were investigated using X-ray diffraction (XRD) and atomic pair distribution function (PDF) methods. An AMC with a hydromagnesite-like structure (AMC-I) was formed immediately after mixing MgCl2 and Na2CO3 solutions. After 5 min of stirring, no change was observed in the XRD pattern; however, the PDF pattern changed. This suggests that the medium-range ordered structure of AMC-I transformed into an intermediate structure (AMC-II) between AMC-I and NSQ. After 10 min of stirring, the AMC-II crystallized into NSQ. In the case of Rb2CO3, the AMC-II structure was formed immediately after the mixing of solutions and was stable for three days. AMC-II in the Rb2CO3 solution appeared to be in equilibrium with energetic local minima, indicating the existence of polyamorphism in AMC. When Cs2CO3 solution was used, the first precipitate had an AMC-I structure. By stirring for 5 min, the AMC-I was transformed to AMC-II, and after 10 min of stirring, a few quantities crystallized into NSQ. After three days, NSQ dissolved and transformed back into AMC-I. Thus, it is inferred that the crystallization of NSQ is significantly influenced by alkali cations in aqueous solutions. The AMC formed during the thermal decomposition also possesses the AMC-I structure.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data Availability
The data that support the findings of this study are available from the corresponding author upon reasonable request.
References
Akao M, Iwai S (1977) The hydrogen bonding of hydromagnesite. Acta Crystallogr B Struct Crystallogr Cryst Chem 33:1273–1275. https://doi.org/10.1107/S0567740877005834
Aminu MD, Nabavi SA, Rochelle CA, Manovic V (2017) A review of developments in carbon dioxide storage. Appl Energy 208:1389–1419. https://doi.org/10.1016/j.apenergy.2017.09.015
Bachu S, Gunter WD, Perkins EH (1994) Aquifer disposal of CO2: hydrodynamic and mineral trapping. Energy Convers Manag 35:269–279. https://doi.org/10.1016/0196-8904(94)90060-4
Back ME, Mandarino JA (2008) Fleischer’s glossary of mineral species. Mineralogical Record Inc., Tucson
Ballirano P, De Vito C, Ferrini V, Mignardi S (2010) The thermal behaviour and structural stability of nesquehonite, MgCO3·3H2O, evaluated by in situ laboratory parallel-beam X-ray powder diffraction: new constraints on CO2 sequestration within minerals. J Hazard Mater 178:522–528. https://doi.org/10.1016/j.jhazmat.2010.01.113
Ballirano P, De Vito C, Mignardi S, Ferrini V (2013) Phase transitions in the MgCO2H2O system and the thermal decomposition of dypingite, Mg5(CO3)4(OH)2·5H2O: implications for geosequestration of carbon dioxide. Chem Geol 340:59–67. https://doi.org/10.1016/j.chemgeo.2012.12.005
Beinlich A, Austrheim H (2012) In situ sequestration of atmospheric CO2 at low temperature and surface cracking of serpentinized peridotite in mine shafts. Chem Geol 332–333:32–44. https://doi.org/10.1016/j.chemgeo.2012.09.015
Bhattacharjya D, Selvamani T, Mukhopadhyay I (2012) Thermal decomposition of hydromagnesite. J Therm Anal Calorim 107:439–445. https://doi.org/10.1007/s10973-011-1656-9
DECC (2012) CCS Road map—supporting deployment of carbon capture and storage in the UK. Department of Energy & Climate Change, Crown, London, pp 1–50
Di Lorenzo F, Rodríguez-Galán RM, Prieto M (2014) Kinetics of the solvent-mediated transformation of hydromagnesite into magnesite at different temperatures. Miner Mag 78:1363–1372. https://doi.org/10.1180/minmag.2014.078.6.02
Farrow CL, Juhas P, Liu JW, Bryndin D, Božin ES, Bloch J, Proffen T, Billinge SJL (2007) PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals. J Phys Condens Matter 19:335219. https://doi.org/10.1088/0953-8984/19/33/335219
Frost RL, Bahfenne S, Graham J, Reddy BJ (2008) The structure of selected magnesium carbonate minerals—a near infrared and mid-infrared spectroscopic study. Polyhedron 27:2069–2076. https://doi.org/10.1016/j.poly.2008.03.019
Gebauer D, Gunawidjaja PN, Ko JYP, Bacsik Z, Aziz B, Liu LJ, Hu YF, Bergström L, Tai CW, Sham TK, Edén M, Hedin N (2010) Proto-calcite and proto-vaterite in amorphous calcium carbonates. Angew Chem Int Ed Engl 49:8889–8891. https://doi.org/10.1002/anie.201003220
Giester G, Lengauer CL, Rieck B (2000) The crystal structure of nesquehonite, MgCO3·3H2O, from Lavrion, Greece. Miner Petrol 70:153–163. https://doi.org/10.1007/s007100070001
Hänchen M, Prigiobbe V, Baciocchi R, Mazzotti M (2008) Precipitation in the Mg-carbonate system - effects of temperature and CO2 pressure. Chem Eng Sci 63:1012–1028. https://doi.org/10.1016/j.ces.2007.09.052
Hopkinson L, Kristova P, Rut K, Cressey G (2012) Phase transitions in the system MgO-CO2-H2O during CO2 degassing of Mg-bearing solutions. Geochim Cosmochim Acta 76:1–13. https://doi.org/10.1016/j.gca.2011.10.023
Hunt JM (1972) Distribution of carbon in crust of earth. Am Assoc Petrol Geol Bull 56:2273–2277
Jauffret G, Morrison J, Glasser FP (2015) On the thermal decomposition of nesquehonite. J Therm Anal Calorim 122:601–609. https://doi.org/10.1007/s10973-015-4756-0
Jensen ACS, Imberti S, Habraken WJEM, Bertinetti L (2020) Small ionic radius limits magnesium water interaction in amorphous calcium/magnesium carbonates. J Phys Chem C 124:6141–6144. https://doi.org/10.1021/acs.jpcc.9b11594
Kloprogge JT, Martens WN, Nothdurft L, Duong LV, Webb GE (2003) Low temperature synthesis and characterization of nesquehonite. J Mater Sci Lett 22:825–829. https://doi.org/10.1023/A:1023916326626
Kristova P, Hopkinson LJ, Rutt KJ, Hunter HMA, Cressey G (2014) Carbonate mineral paragenesis and reaction kinetics in the system MgO-CaO-CO2-H2O in presence of chloride or nitrate ions at near surface ambient temperatures. Appl Geochem 50:16–24. https://doi.org/10.1016/j.apgeochem.2014.08.005
Oelkers EH, Gislason SR, Matter J (2008) Mineral carbonation of CO2. Elements 4:333–337. https://doi.org/10.2113/gselements.4.5.333
Perchiazzi N, Merlino S (2006) The malachite–rosasite group: crystal structures of glaukosphaerite and pokrovskite. Eur J Miner 18:787–792. https://doi.org/10.1127/0935-1221/2006/0018-0787
Qiu X, Thompson JW, Billinge SJL (2004) PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data. J Appl Crystallogr 37:678. https://doi.org/10.1107/S0021889804011744
Radha AV, Fernandez-Martinez A, Hu YD, Jun YS, Waychunas GA, Navrotsky A (2012) Energetic and structural studies of amorphous Ca1−xMgxCO3·nH2O (0 ≤ x ≤ 1). Geochim Cosmochim Act 90:83–95. https://doi.org/10.1016/j.gca.2012.04.056
Reeder RJ (1983) Crystal chemistry of the rhombohedral carbonates. In: Reeder RJ (ed) Carbonates: mineralogy and chemistry. Rev mineral 11. Mineralogical Communications Society of America, Washington, pp 1–47
Ren HR, Chen Z, Wu YL, Yang MD, Chen J, Hu HS, Liu J (2014) Thermal characterization and kinetic analysis of nesquehonite, hydromagnesite, and brucite, using TG-DTG and DSC techniques. J Therm Anal Calorim 115:1949–1960. https://doi.org/10.1007/s10973-013-3372-0
Rodriguez-Blanco JD, Shaw S, Benning LG (2011) The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite. Nanoscale 3:265–271. https://doi.org/10.1039/c0nr00589d
Sanna A, Uibu M, Caramanna G, Kuusik R, Maroto-Valer MM (2014) A review of mineral carbonation technologies to sequester CO2. Chem Soc Rev 43:8049–8080. https://doi.org/10.1039/c4cs00035h
Seto Y, Nishio-Hamane D, Nagai T, Sata N (2010) Development of a software suite on X-ray diffraction experiments. Rev High Press Sci Technol 20:269–276. https://doi.org/10.4131/jshpreview.20.269
Tanaka J, Kawano J, Nagai T, Teng H (2019) Transformation process of amorphous magnesium carbonate in aqueous solution. J Miner Petrol Sci 114:105–109. https://doi.org/10.2465/jmps.181119b
Tobler DJ, Rodriguez Blanco JD, Sørensen HO, Stipp SLS, Dideriksen K (2016) Effect of pH on amorphous calcium carbonate structure and transformation. Cryst Growth Des 16:4500–4508. https://doi.org/10.1021/acs.cgd.6b00630
Wang Y, Li ZB, Demopoulos GP (2008) Controlled precipitation of nesquehonite (MgCO3·3H2O) by the reaction of MgCl2 with (NH4)2CO3. J Cryst Growth 310:1220–1227. https://doi.org/10.1016/j.jcrysgro.2008.01.002
White CE, Henson NJ, Daemen LL, Hartl M, Page K (2014) Uncovering the true atomic structure of disordered materials: the structure of a hydrated amorphous magnesium carbonate (MgCO3·3D2O). Chem Mater 26:2693–2702. https://doi.org/10.1021/cm500470g
Yamamoto G, Kyono A, Abe J, Sano-Furukawa A, Hattori T (2021a) Crystal structure of nesquehonite, MgCO3·3H(D)2O by neutron diffraction and effect of pH on structural formulas of nesquehonite. J Miner Petrol Sci 116:96–103. https://doi.org/10.2465/jmps.200117
Yamamoto G, Kyono A, Sano Y, Matsushita Y, Yoneda Y (2021b) In situ and ex situ studies on thermal decomposition process of hydromagnesite Mg5(CO3)4(OH)2·4H2O. J Therm Anal Calorim 144:599–609. https://doi.org/10.1007/s10973-020-09618-7
Yamamoto G, Kyono A, Okada S (2021c) Temperature dependence of amorphous magnesium carbonate structure studied by PDF and XAFS analyses. Sci Rep 11:22876. https://doi.org/10.1038/s41598-021-02261-8
Yamamoto G, Kyono A, Okada S (2022) Thermal decomposition process of dypingite Mg5(CO3)4(OH)2·5H2O. Mater Lett 308:131125. https://doi.org/10.1016/j.matlet.2021.131125,131125
Zhang ZP, Zheng YJ, Ni YW, Liu ZM, Chen JP, Liang XM (2006) Temperature- and pH-dependent morphology and FT-IR analysis of magnesium carbonate hydrates. J Phys Chem B 110:12969–12973. https://doi.org/10.1021/jp061261j
Acknowledgements
The authors would like to thank two anonymous reviewers for their constructive comments that helped improve the manuscript. PDF measurements performed at BL22XU of SPring-8 were approved by the Photon Factory Program Advisory Committee (Proposal No. 2021A3737). This work was supported by JSPS KAKENHI Grant number JP20K04124).
Funding
This work was supported by Atsushi Kyono: Supported by JSPS KAKENHI (, Ggrant number JP20K04124) granted to Atsushi Kyono.
Author information
Authors and Affiliations
Contributions
GY: Sample preparation, Synchrotron X-ray measurement, Data analysis, and Writing; AK: Supervision, Synchrotron X-ray measurement, Data analysis, Funding acquisition, and Writing—review and editing; SO: Synchrotron X-ray measurement; All authors reviewed and approved the manuscript.
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Ethical approval
Not applicable.
Informed consent
Not applicable.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Yamamoto, Gi., Kyono, A. & Okada, S. Structural variations of amorphous magnesium carbonate during nucleation, crystallization, and decomposition of nesquehonite MgCO3·3H2O. Phys Chem Minerals 50, 5 (2023). https://doi.org/10.1007/s00269-022-01231-4
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00269-022-01231-4