In this work, a study of detection systems in portable X-ray fluorescence (PXRF) spectrometry was performed. An assessment of various detectors and their influence on the measurement of trace elements in different bulk materials, from light to heavy matrices, was done. Four reference materials were analyzed: Orchard Leaves (NBS-1571); Bone Meal (NIST-1486); River Sediment (NBS-1645) and Free-Cutting Brass (NBS-1105). Detection limits were calculated for the elements present in the reference materials, quantitative calculations were performed for three known samples and a comparison was made for each detector. Three case studies were also performed in order to appraise the behavior of the detection systems: A paper document from 1909, a potassium alum/calcite mixture and a Portuguese coin.