Nanolayer stacks are technologically very relevant for current and future applications in many fields of research. A non-destructive characterization of such systems is often performed using X-ray reflectometry (XRR). For complex stacks of multiple layers, low electron density contrast materials or very thin layers without any pronounced angular minima, this requires a full modeling of the XRR data. As such modeling is using the thicknesses, the densities and the roughnesses of each layer as parameters, this approach quickly results in a large number of free parameters. In consquence, cross-correlation effects or interparameter dependencies can falsify the modeling results. Here, we present a route for validation of such modeling results which is based on the reference-free grazing incidence X-ray fluorescence (GIXRF) methodology. In conjunction with the radiometrically calibrated instrumentation of the Physikalisch-Technische Bundesanstalt the method allows for reference-free quantification of the elemental mass depositions. In addition, a modeling approach of reference-free GIXRF-XRR data is presented, which takes advantage of the quantifiable elemental mass depositions by distributing them depth dependently. This approach allows for a reduction of the free model parameters. Both the validation capabilities and the combined reference-free GIXRF-XRR modeling are demonstrated using several nanoscale layer stacks consisting of HfO$_2$ and Al$_2$O$_3$ layers.
