A combination of X-ray diffraction with anomalous X-ray scattering at the Ge K edge and specular reflectivity measurements is used to reveal both composition and atomic ordering in Ge:Si wetting layers. By comparing the intensity distribution close to the (400) and (200) surface reflections we show that the Ge wetting layer is composed of a SiGe alloy which exhibits atomic ordering. Due to the Si interdiffusion the wetting layer thickness is larger than the nominal 3 ML Ge deposition. The chemical depth distribution is obtained from X-ray reflectivity measurements and confirms the enhanced Ge interdiffusion. These phenomena evidence the crucial interplay between surface kinetics and intermixing in SiGe thin films and nanostructures on Si(001) substrates. (c) 2006 Elsevier B.V. All rights reserved.