Wavelength dispersive X‐ray fluorescence spectrometry (WD‐XRF) is widely used for the analysis of soils and sediments using well characterised procedures. However, difficulties can occur with samples such as unknowns containing small amounts of ore materials and samples collected from contaminated sites where trace elemental concentrations can exceed the concentration range for routine analysis. We studied the performance of a commercially available method, based on fundamental parameters (FP) to correct matrix effects. The spectrometer was originally calibrated with elemental or simple compound calibrants. Samples were analysed as pressed powder pellets. Eighteen sediment and soil reference materials, three of them with certified values for some of their constituents, were used to evaluate accuracy, by comparing results with recommended values and their standard deviations (RV ± 2s) or certified values and their confidence intervals (CV ± Cl). When results fell systematically outside these intervals, calibrations were refined with geochemical reference materials. The best agreement of results with recommended and certified values was obtained when the contents of H2O and C in each sample were included as matrix constituents during calculations. The detection limits of trace elements tended to be relatively high, because the measuring conditions employed were not maximised for sensitivity. The main advantage of the method tested was that it enabled the analysis of samples with high concentrations of trace elements and the determination of elements such as F, Bi, Sb and W, which are not commonly included in quantitative XRF analysis of geological samples.