Bergaya F. Handbook of Clay Science

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Manceau, A., Charlet, L., 1992. X-ray adsorption spectroscopic study of Cr(III) at the ox-

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Colloid and Interface Science 148, 425–442.

Manceau, A., Charlet, L., 1994. The mechanism of selenate adsorption on goethite and hy-

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Manceau, A., Combes, J.M., 1988. Structure of Mn and Fe oxides and oxyhydroxides: a

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Manceau, A., Decarreau, A., 1988. Extended X-ray absorption ﬁne-structure study of cobalt-

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Manceau, A., Gates, W.P., 1997. Surface structural model for ferrihydrite. Clays and Clay

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Manceau, A., Bonnin, D., Kasier, P., Fretigny, C., 1988. Polarized EXAFS spectra of biotite

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Manceau, A., Bonnin, D., Stone, W.E.E., Sanz, J., 1990a. Distribution of Fe in the octahedral

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Manceau, A., Chateigner, D., Gates, W.P., 1998. Polarized EXAFS, distance-valence

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Manceau, A., Charlet, L., Boisset, M.C., Didier, B., Spadini, L., 1992a. Sorption and speciat-

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Manceau, A., Gorshkov, A.I., Drits, V.A., 1992c. Structural chemistry of manganese, iron

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Chapter 12.3: X-ray Absorption Spectroscopy856

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Manceau, A., Marcus, M.A., Tamura, N., 2002a. Quantitative speciation of heavy metals in

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Manceau, A., Nagy, K.L., Spadini, L., Ragnarsdottir, K.V., 2000c. Inﬂuence of anionic layer

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Manceau, A., Schlegel, M., 2001. Texture effect on polarized EXAFS amplitude. Physics and

Chemistry of Minerals 28, 52–56.

Manceau, A., Schlegel, M.L., Chateigner, D., Lanson, B., Bartoli, C., Gates, W., 1999a.

Application of polarised EXAFS to ﬁne-grained layered minerals. In: Schulze, D.G.,

Stucki, J.W., Bertsch, P.M. (Eds.), Synchrotron X-ray Methods in Clay Science. CMS

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Manceau, A., Schlegel, M.L., Nagy, K.L., Charlet, L., 1999b. Evidence for the formation of

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Chapter 12.3: X-ray Absorption Spectroscopy864

Handbook of Clay Science

Edited by F. Bergaya, B.K.G. Theng and G. Lagaly

Developments in Clay Science, Vol. 1

865

Chapter 12.4

X-RAY PHOTOELECTRON SPECTROSCOPY

H. SEYAMA

, M. SOMA

b,1

AND B. K.G. THENG

Environmental Chemistry Division, National Institute for Environmental Studies, 16-2

Onogawa, Tsukuba, Ibaraki 305-8506, Japan

Institute for Environmental Sciences, University of Shizuoka, 52-1 Yada, Shizuoka,

Shizuoka 422-8526, Japan

Landcare Research, Palmerston North, New Zealand

The size of clay particles is in the micrometer range. As the speciﬁc surface area of

a particulate assemblage is inversely proportional to the size of its constituent par-

ticles, clays make an important contribution to many processes that occur at the

surface of soil particles. However, even for a particle of micrometer dimensions the

number of atoms exposed at the surface is a small fraction of the total. For example,

in a simple cubic lattice with a lattice constant of 0.2 nm, the fraction of surface-

exposed atoms of a 1 mm cube is only 1.2  10

–3

. For this reason, surface-speciﬁc

analytical techniques are required for assessing the chemical composition of clay

particle surfaces. A general review of these techniques together with their miner-

alogical applications was provided by Hochella (1995).

X-ray photoelectron spectroscopy (XPS) is the single, most versatile technique for

analysing the surface composition of clay mineral particles under different chemical

conditions. XPS can detect almost all elements in the surface layer with sensitivities

not varying by two orders of magnitude, and provide information on chemical

bonding. An added advantage is that XPS is essentially non-destructive even for

materials of high susceptibility. Thus XPS can reveal differences in chemical com-

position between the surface and the bulk, and assess changes in composition and

chemical bonding as a result of surface interactions with other materials.

Here we focus on the application of XPS for characterizing clay and clay mineral

surfaces. An advan ced textbook on the principles and instrumentation of electron

spectroscopy is that by Briggs and Seah (1990). The analysis of clay materials by

XPS was earlier reviewed by Cocke et al. (1994) and Paterson and Swafﬁeld (1994),

while Seyama and Soma (2003) summarized the applic ation of XPS and other sur-

face-analytical techniques in the analysis of geological and environmental samples.

DOI: 10.1016/S1572-4352(05)01030-5

Present Address: 6-8 Tsutsujigaoka, Aoba-ku, Yokohama, kanagawa 227-0055, Japan