Abstract: Continuous wave and pulsed electron paramagnetic resonance spectroscopies combined with thermal and chemical methods were used to identify and characterize V(IV), Fe(III), Mn(II) and Cr(III) in a multimineral system that consists of vermiculite and impurities of carbonates. All of these transition metals were structure-bound in mineral phases. The V(IV) was located in octahedral layers of the vermiculite and became oxidized to V(V) during the transformation of the host mineral to enstatite at about 800 °C. The Fe(III) was associated with the vermiculite as well as the carbonate impurities. The Fe(III) identified in the vermiculite was transferred into the enstatite structure during the thermal conversion. An indirect proof of Fe(III) and Cr(III) in the impurities was found in the heated samples in which these cations occurred in Ca and/or Mg oxides that were formed by transformation of the carbonates. The Mn(II) in the untreated samples was associated with the impurities and was also detected in oxides formed from the samples heated at 600 °C.