Electron paramagnetic resonance and electron spin echo spectroscopy study of natural bornite

Summary A minero-chemical and spectroscopic characterisation has been performed on a natural bornite sample from the Natural History Museum of the University of Florence, through the use of EPMA, XRD, continuous-wave (cw) and pulsed EPR spectroscopy. The use of different EPR techniques allowed to fully investigate the distribution and valence states of Cu and Fe and to study the early oxidation products of bornite. The microanalytical and XRD characterisation proved bornite to be homogeneous and stoichiometric. Cw-EPR measurements confirmed the presence of Fe(III) as fundamental valence state in bornite; moreover, no evidence of Cu(II) as a bulk transient species, due to a charge transfer process, has been revealed. The broadening of the Fe(III) EPR spectrum is ascribed to a partial transfer of spin density from Fe(III) to the surrounding cationic sublattice. In contrast, the pulsed EPR experiments, registered at 4.2 K, revealed the presence of both Fe(III) and Cu(II). These species were supposed to be present at the early stage of the surface alteration. The data provided by the electron spin-echo decay and modulation suggest both the oxidised Cu(II) and Fe(III) species to belong to premature surface water adducts (evidenced by proton nuclear modulation), which may evolve to sulphate species.