The aim of this work was to relate the contribution of mine-derived airborne particulate matter to Ca, Fe, Mn and S content and distribution in Punctelia hypoleucites transplanted to Bajo de la Alumbrera, an important open-pit mine in Catamarca, Argentina. Lichen samples were transplanted to four monitoring sites: two sites inside the mine perimeter and two sites outside the mine. After three months, elemental distribution in samples was analyzed by microparticle-induced X-ray emission (microPIXE), and elemental concentration was determined by specific techniques: Ca and Fe by instrumental neutron activation analysis, Mn by inductively coupled plasma atomic emission spectrometry and S by a turbidimetric method. A differential distribution of S and Ca in thalli transplanted in-mine sites was detected compared to that of samples transplanted outside-mine sites. An overlap of Fe and S in the upper cortex of the apothecium section was observed, leading to infer a mineral association of both elements. Similar association was observed for Ca and S. In addition to these results, the significantly higher concentration detected for S and Mn in in-mine site samples suggests a contribution of Fe, S, Ca and Mn of mining origin to the content and distribution of these elements in P. hypoleucites. MicroPIXE complemented with Mössbauer spectroscopy analysis determined the presence of pyrite particles together with other iron-bearing minerals displaying different degrees of oxidation. These results point to a mining origin of the airborne particulate matter trapped by the lichen thalli transplanted to Bajo de la Alumbrera. These findings indicate that P. Hypoleucites acts as an excellent air quality biomonitor in the Bajo de la Alumbrera mine area.