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Morphological and crystallographic controls in the replacement of calcite and aragonite by cerussite and otavite

Journal Article · · Geochimica et Cosmochimica Acta
 [1];  [1];  [1];  [1]
  1. Argonne National Laboratory (ANL), Argonne, IL (United States)

Mineral replacement reactions are essential solid-fluid interactions in natural and industrial processes including metasomatism, diagenesis, and metamorphism, and sequestration of metal toxins from polluted water. In this paper, we explore the morphological evolution of aragonite and calcite (polymorphs of CaCO3) during their replacement by cerussite (PbCO3, an isomorph of aragonite) and otavite (CdCO3, an isomorph of calcite) in acidic aqueous solutions (with initial pH 3 to 4). Observations using scanning electron and synchrotron-based transmission X-ray microscopies reveal the formation of pseudomorphic shells (~5 to 10 µm thick) of cerussite and otavite when Pb2+ is reacted with either calcite or aragonite and when Cd2+ is reacted with aragonite. The formation of pore space at the substrate-precipitate interface and within the precipitate is found to be key in promoting chemical exchange between the dissolving phase and the solution. In contrast, minimal reactivity is observed when Cd2+ is reacted with calcite. These results demonstrate that the lack of substrate-precipitate epitaxy (either because of inconsistent symmetries or due to large lattice constant mismatch) is a critical factor that enables replacement of primary CaCO3 minerals by Pb- or Cd-bearing secondary minerals while the presence of epitaxial relationships inhibit those reactions. When calcite and aragonite coexist, the replacement of aragonite by cerussite and otavite occurs preferentially over calcite. We postulate that the relative reactivity of calcite and aragonite to Pb2+ and Cd2+ can be determined by interplay between morphological and crystallographic properties of CaCO3 materials as well as solution chemistry. Our results demonstrate that coupled dissolution-precipitation processes of carbonate minerals play an important role in controlling mobility and bioavailability of lead and cadmium in environments where acidic metal-contaminated water interacts with carbonate-rich rocks and soils.

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)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
2426384
Alternate ID(s):
OSTI ID: 1960588
Journal Information:
Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 341; ISSN 0016-7037
Publisher:
Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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