Linked Reactivity at Mineral-Water Interfaces Through Bulk Crystal Conduction
Abstract
The semiconducting properties of a wide range of minerals are often ignored in the study of their interfacial geochemical behavior. We show that surface-specific charge density accumulation reactions combined with bulk charge carrier diffusivity create conditions under which interfacial electron transfer reactions at one surface couple with those at another via current flow through the crystal bulk. Specifically, we observed that a chemically induced surface potential gradient across hematite (α-Fe2O3) crystals is sufficiently high and the bulk electrical resistivity sufficiently low that dissolution of edge surfaces is linked to simultaneous growth of the crystallographically distinct (001) basal plane. The apparent importance of bulk crystal conduction is likely to be generalizable to a host of naturally abundant semiconducting minerals playing varied key roles in soils, sediments, and the atmosphere.
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References and Notes
1
R. T. Shuey, Semiconducting Ore Minerals, vol. 4 of Developments in Economic Geology (Elsevier, Amsterdam, 1975).
2
J. H. Kennedy, K. W. Frese, J. Electrochem. Soc.125, 723 (1978).
3
C. Gleitzer, J. Nowotny, M. Rekas, Appl. Phys. A Mat. Sci. Proc.53, 310 (1991).
4
B. A. Balko, K. M. Clarkson, J. Electrochem. Soc.148, E85 (2001).
5
P. Venema, T. Hiemstra, P. G. Weidler, W. H. van Riemsdijk, J. Colloid Interface Sci.198, 282 (1998).
6
F. Gaboriaud, J. Ehrhardt, Geochim. Cosmochim. Acta67, 967 (2003).
7
C. G. B. Garrett, W. H. Brattain, Phys. Rev.99, 376 (1955).
8
P. Mulvaney, V. Swayambunathan, F. Grieser, D. Meisel, J. Phys. Chem.92, 6732 (1988).
9
R. M. Cornell, U. Schwertmann, The Iron Oxides: Structure, Properties, Reactions, Occurrence and Uses (VCH, Weinheim, Germany, 2003).
10
T. Nakau, J. Phys. Soc. Jpn.15, 727 (1960).
11
N. Iordanova, M. Dupuis, K. M. Rosso, J. Chem. Phys.122, 144305 (2005).
12
J. S. LaKind, A. T. Stone, Geochim. Cosmochim. Acta53, 961 (1989).
13
P. Mulvaney, R. Cooper, F. Grieser, D. Meisel, Langmuir4, 1206 (1988).
14
A. G. B. Williams, M. M. Scherer, Environ. Sci. Tech.38, 4782 (2004).
15
P. Larese-Casanova, M. M. Scherer, Environ. Sci. Tech.41, 471 (2007).
16
D. Suter, C. Siffert, B. Sulzberger, W. Stumm, Naturwissenschaften75, 571 (1988).
17
V. Barron, J. Torrent, J. Colloid Interface Sci.177, 407 (1996).
18
C. M. Egglestonet al., Geochim. Cosmochim. Acta67, 985 (2003).
19
T. P. Trainoret al., Surf. Sci.573, 204 (2004).
20
O. W. Duckworth, S. T. Martin, Geochim. Cosmochim. Acta65, 4289 (2001).
21
T. H. Yoon, S. B. Johnson, C. B. Musgrave, G. E. Brown, Geochim. Cosmochim. Acta68, 4505 (2004).
22
J. R. Rustad, E. Wasserman, A. R. Felmy, Surf. Sci.424, 28 (1999).
23
T. Hiemstra, W. H. Van Riemsdijk, Langmuir15, 8045 (1999).
24
P. Zarzycki, Appl. Surf. Sci.253, 7604 (2007).
25
Materials and methods are available on Science Online.
26
M. J. Avena, O. R. Camara, C. P. Depauli, Colloid Surf.69, 217 (1993).
27
N. Kallay, T. Preocanin, J. Colloid Interface Sci.318, 290 (2008).
28
J. A. Davis, R. O. James, J. O. Leckie, J. Colloid Interface Sci.63, 480 (1978).
29
B. Zinder, G. Furrer, W. Stumm, Geochim. Cosmochim. Acta50, 1861 (1986).
30
S. Banwart, S. Davies, W. Stumm, Colloid Surf.39, 303 (1989).
31
S. Kerisit, K. M. Rosso, Geochim. Cosmochim. Acta70, 1888 (2006).
32
S. Kerisit, K. M. Rosso, J. Chem. Phys.127, 124706 (2007).
33
N. M. Dimitrijevic, D. Savic, O. I. Micic, A. J. Nozik, J. Phys. Chem.88, 4278 (1984).
34
J. P. Jolivet, E. Tronc, J. Colloid Interface Sci.125, 688 (1988).
35
This research was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Geosciences Program. It was performed at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) at the Pacific Northwest National Laboratory (PNNL). The EMSL is funded by the DOE Office of Biological and Environmental Research. PNNL is operated by Battelle for the DOE under contract DE-AC06-76RLO 1830. We gratefully acknowledge the assistance of C. Wang for TEM; B. Arey for scanning electron microscopy; D. McCready for pole reflection x-ray diffraction; Y. Lin for access to electrochemistry apparatus; and A. Felmy, E. Ilton, and J. Amonette for comments on an early version of this manuscript.
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Volume 320 | Issue 5873
11 April 2008
11 April 2008
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American Association for the Advancement of Science.
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Received: 4 January 2008
Accepted: 25 February 2008
Published in print: 11 April 2008
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