This work compared the multi-element analysis of human hair and nails using inductively coupled plasma mass spectrometry (ICP MS) with an easy, fast, cheap, non-destructive method using energy-dispersive x-ray fluorescence (ED XRF). The ICP MS-based method was more sensitive (over 30 elements could be quantified) and costly (requiring more time, samples, and chemicals). The EDX-based method required laboratory and certified reference materials made of hair for instrument calibration. It was less sensitive (16 elements could be quantified: S, Si, Ca, Br, Fe, Cu, Cr, Mg, Si, K, Mn, Ni, Zn, Se, Sr, Pb), but it allowed us to replace troublesome grinding with the dissolution of keratin-based material with an alkalic agent (tetramethylammonium hydroxide, TMAH) and the formation of stable-for-days pellets. This method is simple, enables automation, and, due to the modification of wells in the autosampler of the EDX system via the immersion of home-designed inserts, it requires smaller amounts of biological material and binder (down to 70 mg instead of 500 mg required by commercially available instrument) to perform analysis. It was concluded that the EDX-based method offers complementary selectivity and sensitivity to ICP MS with the possibility of sample reuse for further analysis.
Keywords: ED XRF; ICP MS; hair and fingernails; metal determination; pellet formation; solubilization of keratin.