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A X-ray photoelectron Fe 2p 3/2  spectrum of a pristine pyrite fracture surface was collected using synchrotron radiation with the source tuned to 800 eV. Comparison of this highly surface sensitive Fe 2p spectrum with Fe 2p spectra collected by conventional means (1487 eV AlKa source) reveals that the high binding energy tail of the pyrite Fe 2p 3/2  line results primarily from Fe surface state contributions. The three major contributions to the spectrum are interpreted to be: (1) Fe 2+  resident on bulk sites; (2) Fe 2+  resident on surfaces, edges and corners; (3) Fe 3+  surface states produced during fracture by an auto-redox reaction involving Fe and S. The intense main peak is ascribed to the bulk state, whereas the high binding energy tail of the spectrum is composed primarily of Fe 2+  and Fe 3+  surface state contributions.

Synchrotron XPS evidence for Fe 2+ -S and Fe 3+ -S surface species on pyrite fracture-surfaces, and their 3D electronic states