XSW measurements of single crystal surfaces are performed on a diffractometer. The crystal is rocked through a Bragg diffraction condition, and the reflectivity and XSW yield are simultaneously measured. XSW yield is usually detected as X-ray fluorescence (XRF). XRF detection enables in situ measurements of interfaces between a surface and gas or liquid environments, since hard X-rays can penetrate these media. While XRF gives an element-specific XSW yield, it is not sensitive to the chemical state of the absorbing atom. Chemical state sensitivity is achieved using photoelectron detection, which requires ultra-high vacuum instrumentation.