This paper is based on microprobe analysis (Ta, Nb, Fe, Mn, Ti, W, Sn) and Fe3+ EPR spectra of cassiterite samples from 14 tin deposits from the Iberian Hercynian Massif. The interpretation of microprobe data, atomic ratios (Fe+Mn)/(Nb+Ta), and Fe3+ EPR spectra reveal that the coupled substitution: 3Sn4+ = (Fe,Mn)2+ + 2(Nb,Ta)5+ is dominant in cassiterites from pegmatites, and high-temperature quartz veins and in the dark zones of cassiterites.
2Sn4+ = Fe3+ + (Nb,Ta)5+ and
Sn4+ + O2− = Fe3+ + OH−
are dominant in those from medium-low temperature quartz veins and in the light zones of cassiterites.