First-order derivative of 15 points smoothed chromatograms of mixtures of benzo(b)fluoranthene (BbF) and benzo(k)fluoranthene (BkF) for the m/z 252 ion obtained using two microscans has been proposed as a simple alternative to the resolution of overlapped chromatographic peaks of these two compounds which have identical mass spectra. The procedure provides limits of detection of 12 and 29ngg(-1) for BbF and BkF, respectively and offers the possibility to use the 250 and 248 ions to confirm the identity of these analytes.