An analytical instrument is disclosed having both XRF and spark emission spectroscopy capabilities. In a particularly advantageous embodiment, a field portable XRF device is removably coupled to the instrument by means of a docking station. A first surface of the sample is irradiated with an X-ray beam, and the X-ray radiation fluorescently emitted from the sample is detected and analyzed to acquire elemental composition data. The instrument is further provided with a spark source located proximal a second surface of the sample and a detector for sensing the radiation emitted from the spark-excited material. The combined instrument enables the acquisition of complementary elemental composition data by XRF and spark emission spectroscopy without having to transport a sample between separate instruments.