X-ray fluorescence: where do expelled electrons go?
There are a number of techniques that use excitation of inner shell electrons. Auger spectroscopy, and ESCA for example. But XRF is a "bulk" analysis method, not surface such as Auger. The excitation energy from the initial x-ray will be keV whereas the empty orbitals in the atoms of the sample will be a few eV. The excited electron rips trough the sample creating various ions until its energy is reduced enough so that the emitted electron can drop into some empty low energy orbital. (In general it would a "different" electron that drops into the vacancy and creates the fluorescent x-ray.) 

In general the x-ray can penetrated deeper into the sample than an excited electron can escape. So the bulk of the excited electrons stay within the sample.