Unique information about the chemical vicinity of positron annihilation sites is provided by the contribution of high electron momenta to the Doppler spectrum, since this momentum range is characteristic for the annihilation with core electrons and hence element specific. However, the corresponding energy region in the spectrum is overlaid by a huge background caused by the annihilation radiation itself and the Compton spectrum of other gamma lines having an energy above 511 keV. Usually these backgrounds are reduced by measuring both annihilation quanta in coincidence. By mathematically analyzing the background contributions, we open another possibility to obtain the high-momentum region employing one single germanium detector. A necessary precondition is employing either background-free positron beams or a low-background positron source, e.g. Ge-68, instead of the widely used positron emitter Na-22. The Ge-68-source emits positrons with an endpoint energy of about 1.9 MeV, where as the contribution of gamma quanta having higher energies than the annihilation radiation at 511 keV is negligible low. When analyzing spectra from metals and semiconductors according to the described background subtraction, the same information contained in the momentum range up to 35 x 10(3)m(0)c or beyond can be extracted, as if the spectra were measured employing a coincidence setup with two Ge-detectors. (C) 2008 Elsevier B.V. All rights reserved.