Within the first nine months following the activation of the GPS radio occultation experiment aboard the low Earth orbiting satellite CHAMP, more than 25,000 occultation events have been observed. A radio holographic analysis of 3783 occultation events, recorded between 14 May 2001 and 10 June 2001, reveals that in about 20--30% of these events the received signal contains contributions from components reflected at Earth's surface. On the basis of geometrical ray tracing and multiple phase screen calculations, characteristic frequency shifts in the radio holograms' power spectral densities are analyzed quantitatively. These frequency shifts are found to be dominated by surface elevation at the reflection point location and ground-level refractivity. Using temperature and pressure profiles from European Centre for Medium-Range Weather Forecasting (ECMWF) analyses, ground-level specific humidities are derived in good agreement with ECMWF values. Complex patterns found in radio hologram spectra within a subset of observations at low latitudes are interpreted in terms of multipath propagation caused by layered structures in the refractivity field.