Abstract: The 57Fe Mössbauer spectra of a series of untreated and Ca-saturated nontronites showed a predominant Fe3+ resonance which was computer-fitted with two Fe3+ doublets defining iron in non-equivalent cis-FeO4(OH)2 octahedral sites. In most spectra a doublet indicating tetrahedral Fe3+ was fitted and in one untreated sample a doublet indicating interlayer Fe3+ was identified. In a further untreated sample the interlayer iron was present as Fe2+. Upon Ca-saturation the interlayer iron was displaced. It also appears that the interlayer iron was present in at least two different interlayer sites. From the computer-fitted data it was clear that the interlayer cations have a significant effect on the Mössbauer resonances of iron in the two non-equivalent cis-octahedral and the tetrahedral sites of nontronite.