Pb 2+–Calcite Interactions under Far-from-Equilibrium Conditions: Formation of Micropyramids and Pseudomorphic Growth of Cerussite
Abstract
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:
-
[1];
[1];
[1]
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of Delaware, Newark, DE (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
- OSTI Identifier:
- 1426695
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Journal Article: 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
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
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., 2018.
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. Thu .
"Pb2+–Calcite Interactions under Far-from-Equilibrium Conditions: Formation of Micropyramids and Pseudomorphic Growth of Cerussite". United States. doi:10.1021/acs.jpcc.7b11682. https://www.osti.gov/servlets/purl/1426695.
@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},
issn = {1932-7447},
number = 4,
volume = 122,
place = {United States},
year = {2018},
month = {1}
}
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Figure 1.: “Spiky” vs. smooth calcite crystals. SEM images of calcite crystals of two different orientations (a, b “lying down” vs. c, d “standing up”) reacted in (a, c) 5 mM Pb2+ solution having initial pH = 2.8 and in (b, d) Pb-free solution having initial pH = 2.8 formore »
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