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Morphology of Lead(II) and Chromium(III) Reaction Products on Phyllosilicate Surfaces As Determined By Atomic Force Microscopy

Published online by Cambridge University Press:  28 February 2024

Huamin Gan ,
George W. Bailey  and
Y. Shane Yu
Huamin Gan*
Affiliation:
National Research Council, U.S. Environmental Protection Agency, 960 College Station Road, Athens, Georgia 30605-2700
George W. Bailey
Affiliation:
Ecosystems Research Division, National Exposure Research Laboratory, U.S. Environmental Protection Agency, 960 College Station Road, Athens, Georgia 30605-2700
Y. Shane Yu*
Affiliation:
Dyn-Corp-Technology Applications, Inc., 960 College Station Road, Athens, Georgia 30605-2700
*
†Current Address: Engelhard Corporation, P.O. Box 337, Gordon, Georgia 31031.
‡Current Address: Equifax, Inc., Decision Systems, External Mail Drop 425, 1525 Windward Concourse, Alpharetta, Georgia 30202.
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Abstract

Redox and acid-base reactions play important roles in the fate of metal contaminants in soils and sediments. The presence of significant amounts of Cr, Pb and other toxic heavy metals in contaminated soils and sediments is of great environmental concern. Oxidation states and dissolution characteristics of the heavy metals can exert negative effects on the natural environment. Atomic force microscopy (AFM) was used to follow the changes in morphology and structure of reaction products of Cr and Pb formed on mineral surfaces. Nitrate salts of Cr(III) and Pb(II) were used to replace the native exchangeable cations on muscovite and smectite surfaces and the metal-mineral systems were then reacted at different pH's and redox conditions.

For Pb, aggregate morphological forms were found at pH 6.1 and 12.4. At pH 6.1, the mean roughness value was 0.70 nm, and at pH 12.4 it was 5.30 nm. The fractal dimensions were 2.03 at pH 6.1 and 2.05 at pH 12.4. For Cr(III), both layered and aggregate morphological forms were found at pH 6.8 and 10.8. The mean roughness values were 0.90 nm at pH 6.8 and 4.3 nm at pH 10.8. Fractal dimensions for both were 2.00. The effect of redox conditions on morphological characteristics was studied on a smectite substrate. The reduced clays were more compacted than oxidized ones and the reduced clay could reduce Cr(VI) to Cr(III), forming new minerals on the surfaces.

A geochemical equilibrium model, MINTEQA2, was used to simulate the experimental conditions and predict possible reaction products. Simulation results agreed well with data from experiments, providing evidence that modeling can provide a useful “reality check” for such studies. Together, MINTEQA2 and AFM can provide important information for evaluating the morphologies and chemical reactivities of metal reaction products formed on phyllosilicate surfaces under varying environmental conditions.

Keywords

Atomic Force MicroscopyClayFTIRGeochemical Equilibrium ModelMicaRemediationSmectiteX-ray
Type
Research Article
Information
Clays and Clay Minerals , Volume 44 , Issue 6 , December 1996 , pp. 734 - 743
Copyright
Copyright © 1996, The Clay Minerals Society

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References

Albrecht, T.R. and Quate, C.F.. 1987. Atomic resolution imaging of nonconductor by atomic force microscopy. J Appl Phys 62: 2599–2602.CrossRefGoogle Scholar
Allison, J.D., Brown, D.S. and Novo-Gradac, K.J.. 1991. MINTEQA2/PRODEFA2, A geochemical assessment model for environmental systems: version 3.0 user's manual. Athens, GA: US EPA. EPA/600/3-91/021. 106 p.Google Scholar
Avnir, D.. 1989. The fractal approach to heterogeneous chemistry: surfaces, colloids and polymers. New York: J Wiley. 441 p.Google Scholar
Baes, C.F. Jr. and Mesmer, R.E.. 1976. The hydrolysis of cations. New York: J Wiley. 489 p.Google Scholar
Bartlett, R.J. and James, B.R.. 1988. Mobility and bioavailability of chromium in soils. In: Niagu, J.O., Nieboer, E., editors. Chromium in the natural and human environments. New York: J Wiley. p 267–304.Google Scholar
Binnig, G., Quate, C.F. and Weibel, E.. 1986. Atomic force microscope. Phys Rev Lett 56: 930–933.CrossRefGoogle ScholarPubMed
Binnig, G., Roher, H., Gerber, C.H. and Weibel, E.. 1982. Tunneling through a controllable vacuume gap. Appl Phys Lett 40: 178–180.CrossRefGoogle Scholar
Burns, V.M. and Burns, R.G.. 1975. Mineralogy of chromium. Geo-chim Cosmochim Acta 39: 903–910.CrossRefGoogle Scholar
Burrough, P.A.. 1989. Fractals and geochemistry. In: Avnir, D., editor. The fractal approach to heterogeneous chemistry: surfaces, colloids and polymers. New York: J Wiley. p 383–406.Google Scholar
Chen, S.Z., Low, P.F. and Roth, C.B.. 1987. Relation between potassium fixation and the oxidation state of octahedral iron. Soil Sci Soc Am J 51: 82–86.CrossRefGoogle Scholar
Cohen, M.D., Kargacin, B. and Klein, C.B.. 1993. Mechanisms of chromium carcinogenicity and toxicity. Critical Rev Toxicol 23(3): 255–281.CrossRefGoogle ScholarPubMed
Cranston, R.E. and Murray, J.W.. 1980. Chromium species in the Columbia River and estuary. Limnol Ocean 25: 1104–1112.CrossRefGoogle Scholar
Drake, B., Prater, C.B., Weisenhorn, A.L., Gould, S.A.C., Albrecht, T.R., Quate, C.F., Cannell, D.S., Hansma, H.G. and Hansma, P.K.. 1989. Imaging crystals, polymers, and processes in water with atomic force microscope. Science 243: 1586–1589.CrossRefGoogle ScholarPubMed
Dreiss, S.J.. 1986. Chromium migration through sludge-treated soils. Ground Water 24: 312–321.CrossRefGoogle Scholar
Elderfield, E.. 1970. Chromium speciation in sea water. Earth Planet Sci Lett 9: 10–16.CrossRefGoogle Scholar
Ewers, U. and Schlipköter, H.W. 1991. Lead. In: Merian, E., editor. Metals and their compounds in the environment. New York: VCH. p 971–1014.Google Scholar
Golovchenko, J.A.. 1986. Tunneling microscopy: a new look at the atomic world. Science 232: 48–53.CrossRefGoogle Scholar
Hansma, P.K., Elings, V.B., Marti, O. and Bracker, C.E.. 1988. Scanning tunneling microscopy and atomic force microscopy: application to biology and technology. Science 242: 209–216.CrossRefGoogle ScholarPubMed
Hansma, P.K. and Tersoff, J.. 1987. Scanning tunneling microscopy. J Appl Phys 61: R1–R23.CrossRefGoogle Scholar
Hartman, H., Sposito, G., Yang, A., Manne, S., Gould, S.A.C. and Hansma, P.K.. 1990. Molecular-scale imaging of clay mineral surfaces with the atomic force microscope. Clays Clay Miner 38: 337–342.CrossRefGoogle Scholar
Hochella, M.F. Jr. 1988. Auger electron and x-ray photoelectron spectroscopies. In: Hawthorne, F.C., editor. Reviews in mineralogy, vol 18, Spectroscopic methods in mineralogy and geology. Washington, DC: Mineralogical Society of America. p 573–673.CrossRefGoogle Scholar
Hochella, M.F. Jr., Eggleston, C.M., Elings, V.B., Parks, G.A., Brown, G.E., Wu, C.M. and Kjoller, K.. 1989. Mineralogy in two dimensions: scanning tunneling microscopy of semiconducting minerals with implications on geochemical reactivity. Am Mineral 74: 1233–1246.Google Scholar
Lear, P.R. and Stucki, J.W.. 1985. The role of structural hydrogen in the reduction and reoxidation of iron in nontronite. Clays Clay Miner 33: 53.9-545.CrossRefGoogle Scholar
Lear, P.R. and Stucki, J.W.. 1987. Intervalence electron transfer and magnetic exchange interactions in reduced nontronite. Clays Clay Miner 35: 373–378.CrossRefGoogle Scholar
Lear, P.R. and Stucki, J.W.. 1989. Effects of iron oxidation state on the specific surface area of nontronite. Clays Clay Miner 37: 547–552.CrossRefGoogle Scholar
Lear, P.R. and Stucki, J.W.. 1990. Magnetic ordering and site occupancy of iron in nontronite. Clay Miner 25: 3–13.CrossRefGoogle Scholar
Lovejoy, S., Shertzer, D. and Tsonis, A.A.. 1987. Functional box-counting and multiple elliptical dimension in rain. Science 235: 1036–38.CrossRefGoogle ScholarPubMed
Mandelbrot, B.B.. 1977. Fractal, form, chance and dimension. San Francisco, CA: Freeman. 365 p.Google Scholar
Mandelbrot, B.B.. 1982. The fractal geometry of nature. San Francisco, CA: Freeman. 573 p.Google Scholar
Nieboer, E. and Jusys, A.A.. 1988. Biologic chemistry of chromium. In: Niagu, J.O., Nieboer, E., editors. Chromium in the natural and human environments, vol 20. New York: J Wiley. p 21–79.Google Scholar
Radoslovich, E.W.. 1959. Structural control of polymorphism in micas. Nature 183: 253.CrossRefGoogle Scholar
Radoslovich, E.W.. 1960. The structure of muscovite, KAl2(Si3Al) O10(OH)2. Acta Crystallogr 13: 919–932.CrossRefGoogle Scholar
Radoslovich, E.W.. 1961. Surface symmetry and cell dimensions of layer lattice silicates. Nature 191: 67–68.CrossRefGoogle Scholar
Radoslovich, E.W. and Norrish, K.. 1962. The cell dimensions and symmetry of layer-lattice silicates. I. Some structural considerations. Am Mineral 47: 599–616.Google Scholar
Stucki, J.W.. 1988. Structural iron in smectites. In: Stucki, J.W., Goodman, B.A., Schwertmann, U., editors. Iron in soils and clay minerals. Dordrecht, Germany: D Reidel. p 625–675.CrossRefGoogle Scholar
Stucki, J.W., Golden, D.C. and Roth, C.B.. 1984. Effect of reduction and reoxidation of structural iron on the surface charge and dissolution of dioctahedral smectites. Clays Clay Miner 32: 350–356.CrossRefGoogle Scholar
Stucki, J.W., Low, P.F., Roth, C.B. and Golden, D.C.. 1984. Effect of oxidation state of octahedral iron on clay swelling. Clays Clay Miner. 32: 357–362.CrossRefGoogle Scholar
Stucki, J.W. and Tessier, D.. 1991. Effects of iron oxidation state on the texture and structural order of Na-nontronite. Clays Clay Miner 39: 137–143.CrossRefGoogle Scholar
Tennyson, C.H.. 1961. The morphology of eskolaite, Cr2O3. Am Mineral 46: 998–999.Google Scholar
Tersoff, J. and Hamann, D.R.. 1983. Theory and application for the scanning tunneling microscope. Phys Rev Lett 50(25): 1998–2001.CrossRefGoogle Scholar
US Environmental Protection Agency. 1988. Identification and listing of hazardous waste. 40 CFR Part 261.Google Scholar
Van Hove, M.A., Weinberg, W.H. and Chan, C.M.. 1986. Low-energy electron diffraction: experiment, theory and surface structure determination. New York: Springer-Verlag. 603 p.CrossRefGoogle Scholar
Wu, J., Low, P.F. and Roth, C.B.. 1989. Effect of octahedral-iron reduction and swelling pressure on interlayer distances in Na-nontronite. Clays Clay Miner 37: 211–218.Google Scholar