Volcanoes produce and release large amounts of toxicants, and the concentration of metals in hair can be used as a biomarker of exposure to trace metals. In order to investigate whether humans exposed to volcanic emissions demonstrate higher concentrations of essential and non-essential trace metals, scalp hair of men (3-89 years) living in two areas of the Azores, one exposed to volcanic emissions and the other not, was sampled, and their content in Cd, Cu, Pb, Rb, Se, and Zn was quantified by using High Resolution Inductively Coupled Plasma Mass Spectrometry. In average, men exposed to volcanic emissions presented higher concentrations of Cd (96.9 ppb), Cu (16.2 ppm), Pb (3417.6 ppb), Rb (216.3 ppb), and Zn (242.8 ppm), but not Se (469.6 ppb). Also, strong and significant correlations were found between Cd-Rb and Pb-Rb in the exposed men. In conclusion, humans living chronically exposed to volcanic emissions show high concentrations of essential and non-essential trace metals in scalp hair, and is suggested that this type of exposure may be as harmful as living close to industrial facilities.