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Title: Pb 2+–Calcite Interactions under Far-from-Equilibrium Conditions: Formation of Micropyramids and Pseudomorphic Growth of Cerussite

The presence of impurity ions is known to significantly influence mineral surface morphology during crystal growth from aqueous solution, but knowledge on impurity ion-mineral interactions during dissolution under far-from equilibrium conditions remains limited. Here we show that calcite (CaCO 3) exhibits a rich array of dissolution features in the presence of Pb. During the initial stage, calcite exhibits non-classical surface features characterized as micro pyramids developed spontaneously in acidic Pb-bearing solutions. Subsequent pseudomorphic growth of cerussite (PbCO 3) was observed, where nucleation occurred entirely within a pore space created by dissolution at the calcite/substrate interface. Uneven growth rates yielded a cerussite shell made of lath- or dendritic-shaped crystals. The cerussite phase was separated from the calcite by pores of less than 200 nm under transmission X-ray microscopy, consistent with the interface-coupled dissolution-precipitation mechanism. These results show that impurity metal ions exert significant control over the microscale dissolution features found on mineral surfaces and provide new insights into interpreting and designing micro structures observed in naturally-occurring and synthetic carbonate minerals by dissolution. In addition, heterogeneous micro-environments created in transport limited reactions under pore spaces may lead to unusual growth forms during crystal nucleation and precipitation.
Authors:
ORCiD logo [1] ;  [1] ;  [1] ;  [2] ; ORCiD logo [1] ; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of Delaware, Newark, DE (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 4; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
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
OSTI Identifier:
1426695

Yuan, Ke, De Andrade, Vincent, Feng, Zhange, Sturchio, Neil C., Lee, Sang Soo, and Fenter, Paul. Pb2+–Calcite Interactions under Far-from-Equilibrium Conditions: Formation of Micropyramids and Pseudomorphic Growth of Cerussite. United States: N. p., Web. doi:10.1021/acs.jpcc.7b11682.
Yuan, Ke, De Andrade, Vincent, Feng, Zhange, Sturchio, Neil C., Lee, Sang Soo, & Fenter, Paul. Pb2+–Calcite Interactions under Far-from-Equilibrium Conditions: Formation of Micropyramids and Pseudomorphic Growth of Cerussite. United States. doi:10.1021/acs.jpcc.7b11682.
Yuan, Ke, De Andrade, Vincent, Feng, Zhange, Sturchio, Neil C., Lee, Sang Soo, and Fenter, Paul. 2018. "Pb2+–Calcite Interactions under Far-from-Equilibrium Conditions: Formation of Micropyramids and Pseudomorphic Growth of Cerussite". United States. doi:10.1021/acs.jpcc.7b11682.
@article{osti_1426695,
title = {Pb2+–Calcite Interactions under Far-from-Equilibrium Conditions: Formation of Micropyramids and Pseudomorphic Growth of Cerussite},
author = {Yuan, Ke and De Andrade, Vincent and Feng, Zhange and Sturchio, Neil C. and Lee, Sang Soo and Fenter, Paul},
abstractNote = {The presence of impurity ions is known to significantly influence mineral surface morphology during crystal growth from aqueous solution, but knowledge on impurity ion-mineral interactions during dissolution under far-from equilibrium conditions remains limited. Here we show that calcite (CaCO3) exhibits a rich array of dissolution features in the presence of Pb. During the initial stage, calcite exhibits non-classical surface features characterized as micro pyramids developed spontaneously in acidic Pb-bearing solutions. Subsequent pseudomorphic growth of cerussite (PbCO3) was observed, where nucleation occurred entirely within a pore space created by dissolution at the calcite/substrate interface. Uneven growth rates yielded a cerussite shell made of lath- or dendritic-shaped crystals. The cerussite phase was separated from the calcite by pores of less than 200 nm under transmission X-ray microscopy, consistent with the interface-coupled dissolution-precipitation mechanism. These results show that impurity metal ions exert significant control over the microscale dissolution features found on mineral surfaces and provide new insights into interpreting and designing micro structures observed in naturally-occurring and synthetic carbonate minerals by dissolution. In addition, heterogeneous micro-environments created in transport limited reactions under pore spaces may lead to unusual growth forms during crystal nucleation and precipitation.},
doi = {10.1021/acs.jpcc.7b11682},
journal = {Journal of Physical Chemistry. C},
number = 4,
volume = 122,
place = {United States},
year = {2018},
month = {1}
}