skip to main content

DOE PAGESDOE PAGES

Title: Replacement of Calcite (CaCO 3) by Cerussite (PbCO 3)

The mobility of toxic elements, such as lead (Pb) can be attenuated by adsorption, incorporation, and precipitation on carbonate minerals in subsurface environments. Here in this paper, we report a study of the bulk transformation of single-crystal calcite (CaCO 3) into polycrystalline cerussite (PbCO 3) through reaction with acidic Pb-bearing solutions. This reaction began with the growth of a cerussite shell on top of calcite surfaces followed by the replacement of the remaining calcite core. The external shape of the original calcite was preserved by a balance between calcite dissolution and cerussite growth controlled by adjusting the Pb 2+ concentration and pH. The relation between the rounded calcite core and the surrounding lath-shaped cerussite aggregates was imaged by transmission X-ray microscopy, which revealed preferentially elongated cerussite crystals parallel to the surface and edge directions of calcite. The replacement reaction involved concurrent development ~100 nm wide pores parallel to calcite c-glide or (1$$\overline{20}$$) planes, which may have provided permeability for chemical exchange during the reaction. X-ray reflectivity measurements showed no clear epitaxial relation of cerussite to the calcite (104) surface. These results demonstrate Pb sequestration through mineral replacement reactions and the critical role of nanoporosity (3% by volume) on the solid phase transformation through a dissolution-recrystallization mechanism.
Authors:
 [1] ;  [1] ;  [2] ;  [3] ;  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  3. Univ. of Delaware, Newark, DE (United States). Dept. of Geological Sciences
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Environmental Science and Technology
Additional Journal Information:
Journal Volume: 50; Journal Issue: 23; Journal ID: ISSN 0013-936X
Publisher:
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Mineral replacement; Transmission X-ray microscopy; calcite
OSTI Identifier:
1368097

Yuan, Ke, Lee, Sang Soo, De Andrade, Vincent, Sturchio, Neil C., and Fenter, Paul. Replacement of Calcite (CaCO3) by Cerussite (PbCO3). United States: N. p., Web. doi:10.1021/acs.est.6b03911.
Yuan, Ke, Lee, Sang Soo, De Andrade, Vincent, Sturchio, Neil C., & Fenter, Paul. Replacement of Calcite (CaCO3) by Cerussite (PbCO3). United States. doi:10.1021/acs.est.6b03911.
Yuan, Ke, Lee, Sang Soo, De Andrade, Vincent, Sturchio, Neil C., and Fenter, Paul. 2016. "Replacement of Calcite (CaCO3) by Cerussite (PbCO3)". United States. doi:10.1021/acs.est.6b03911. https://www.osti.gov/servlets/purl/1368097.
@article{osti_1368097,
title = {Replacement of Calcite (CaCO3) by Cerussite (PbCO3)},
author = {Yuan, Ke and Lee, Sang Soo and De Andrade, Vincent and Sturchio, Neil C. and Fenter, Paul},
abstractNote = {The mobility of toxic elements, such as lead (Pb) can be attenuated by adsorption, incorporation, and precipitation on carbonate minerals in subsurface environments. Here in this paper, we report a study of the bulk transformation of single-crystal calcite (CaCO3) into polycrystalline cerussite (PbCO3) through reaction with acidic Pb-bearing solutions. This reaction began with the growth of a cerussite shell on top of calcite surfaces followed by the replacement of the remaining calcite core. The external shape of the original calcite was preserved by a balance between calcite dissolution and cerussite growth controlled by adjusting the Pb2+ concentration and pH. The relation between the rounded calcite core and the surrounding lath-shaped cerussite aggregates was imaged by transmission X-ray microscopy, which revealed preferentially elongated cerussite crystals parallel to the surface and edge directions of calcite. The replacement reaction involved concurrent development ~100 nm wide pores parallel to calcite c-glide or (1$\overline{20}$) planes, which may have provided permeability for chemical exchange during the reaction. X-ray reflectivity measurements showed no clear epitaxial relation of cerussite to the calcite (104) surface. These results demonstrate Pb sequestration through mineral replacement reactions and the critical role of nanoporosity (3% by volume) on the solid phase transformation through a dissolution-recrystallization mechanism.},
doi = {10.1021/acs.est.6b03911},
journal = {Environmental Science and Technology},
number = 23,
volume = 50,
place = {United States},
year = {2016},
month = {10}
}