Published in

Mineralogical Society of America, American Mineralogist, 2(108), p. 326-337, 2023

DOI: 10.2138/am-2022-8386

Links

Tools

Export citation

Search in Google Scholar

Isotopic responses of magnesium to two types of dissolution-reprecipitation processes for the growth of the double-carbonate mineral norsethite

Journal article published in 2023 by Chuan Liu, Kai Wang, Weiqiang Li ORCID
Distributing this paper is prohibited by the publisher
Distributing this paper is prohibited by the publisher

Full text: Unavailable

Red circle
Preprint: archiving forbidden
Orange circle
Postprint: archiving restricted
Red circle
Published version: archiving forbidden
Data provided by SHERPA/RoMEO

Abstract

Abstract An important mechanism of carbonate mineral growth is dissolution-reprecipitation, including the transformation of amorphous precursor to crystalline carbonates, and coarsening (ripening) of fine carbonate crystals. However, the mechanistic details of cation exchange associated with carbonate mineral growth via a dissolution-reprecipitation process are still not well understood. In this study, we used Mg isotopes to probe the exchange of Mg between aqueous solutions and norsethite [BaMg(CO3)2] by systematic synthesis experiments. Norsethite is a model double carbonate, with a general formula of AB(CO3)2, where A and B stand for two different divalent ions. Formation of norsethite is comprised of three stages, including: (1) precipitation of barium-magnesium (Ba-Mg) amorphous carbonate; (2) transformation of Ba-Mg amorphous carbonate to nano-crystalline norsethite by fast dissolution-reprecipitation; and (3) coarsening (ripening) of nano-norsethite by slow dissolution-reprecipitation. Magnesium isotopes displayed distinct fractionation behaviors in each of the three stages. The Mg isotope fractionation factors (∆26Mgsolid-aq) associated with precipitation of Ba-Mg amorphous carbonate were slightly negative and temperature-dependent, from –0.83‰ at 30 °C to –0.53‰ at 70 °C. During the transformation of Ba-Mg amorphous carbonate to nano-crystalline norsethite, isotopically light Mg isotopes were further enriched in the solid phase, with apparent ∆26Mgsolid-aq decreasing to –2.12‰ at 30 °C and –1.56‰ at 70 °C. In the ripening stage, norsethite became isotopically heavier, with ∆26Mgsolid-aq increasing up to –1.95‰ at 30 °C and –1.17‰ at 70 °C. The experimental results show that non-equilibrium isotope fractionation occurred during the transformation of amorphous carbonate to nano-crystalline norsethite (i.e., fast dissolution-reprecipitation). By contrast, the subsequent ripening of the norsethite led to the evolution toward isotopic equilibrium of the system by slower exchange with a longer reaction time (i.e., slow dissolution-reprecipitation). Moreover, our first-principles calculation results indicate that the equilibrium isotope fractionation was approached, but not attained, even after 276 days of recrystallization at temperatures below 70 °C. In short, this study has identified two different types of dissolution-reprecipitation process during the carbonate mineral growth and highlights the importance of understanding formation mechanism and post-depositional history of carbonate in interpreting the isotopic data of carbonate minerals.