Natural Fe-oxide and -oxyhydroxide nanoparticles: an EPR and SQUID investigation

Magnetic hematite (alpha-Fe2O3) and goethite (alpha-FeOOH) nanoparticles, formed in the abandoned Libiola Mine (Liguria, Italy) as a result of Acid Mine Drainage (AMD) processes that involved sulfide-bearing rocks and sulfide-rich waste material, were investigated through the study of their magnetic properties in combination with electron paramagnetic resonance (EPR) spectroscopy. Both techniques revealed that the behaviour of the nanominerals involved was predominantly superparamagnetic. In contrast, the bulk antiferromagnetic behaviour of both hematite and goethite was substantially reduced. The observed magnetic properties reflected a great variability in the particle dimensions and confirmed that both nanominerals were the transformation products of a metastable amorphous species. Moreover, two peculiar phenomena were hypothesised: the transformation to hematite may occur before the coarsening of the amorphous transient and hematite and goethite can interconvert without intermediate crystallisation of metastable precursors. Goethite, in fact, appears to be formed as an alteration product of hematite, after a drastic change of the physico-chemical boundary conditions.