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Formation of zinc carbonate phases on dissolving calcite, aragonite, and vaterite in acidic aqueous solutions

Journal Article · · Geochimica et Cosmochimica Acta
 [1];  [2];  [3];  [4];  [3];  [2]
  1. Argonne National Laboratory (ANL), Argonne, IL (United States); Pukyong National University, Busan (Korea, Republic of)
  2. Argonne National Laboratory (ANL), Argonne, IL (United States)
  3. University of Delaware, Newark, DE (United States)
  4. Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Calcium carbonate (CaCO3) minerals serve as a major sink to retain metal ions through mineral-water interfacial reactions in which the capacity and long-term stability of contaminant uptake are influenced by coupled dissolution and precipitation reactions of both primary and secondary carbonate minerals (i.e., mineral replacement). Notably, recent studies of calcite reactivity in acidic solutions containing high levels of metal ions demonstrated complex behavior under conditions of sustained disequilibrium. Here, we explored the reactivity of three CaCO3 polymorphs (calcite, aragonite, and vaterite) with acidic Zn2+-containing aqueous solutions using a suite of imaging techniques including optical and scanning electron microscopies, synchrotron-based micro X-ray fluorescence, and transmission X-ray microscopy. Zn uptake by calcite occurred through a two-step process: the formation of a thin layer of the zinc precipitate on the substrate surface followed by the growth of fibrous and radiating hydrozincite particles from the layer. In contrast, Zn uptake by aragonite occurred by mineral replacement where the secondary Zn carbonate phase preserved the external morphology of the original crystal (i.e., a pseudomorph). The replacement of vaterite by hydrozincite occurred within the confined space beneath the porous shell of vaterite, signifying that the primary mechanism driving Zn carbonate precipitation was chemical exchange through the pores. When multiple CaCO3 polymorphs coexisted, the replacement of aragonite and vaterite occurred preferentially over that of calcite. These results demonstrate the distinct morphological and mineralogical controls over the reactivities of calcium carbonate minerals with Zn2+ under acidic conditions.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Research Foundation of Korea (NRF); Ministry of Science and ICT (MSIT)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
2566037
Journal Information:
Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 380; ISSN 0016-7037
Publisher:
Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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