Dissolution reaction and surface iron speciation of UICC crocidolite in buffered solution at pH 7.4: A combined ICP-OES, XPS and TEM investigation

The dissolution reaction and the surface modifications of crocidolite asbestos fibres incubated for 0.5, 1, 24, 48, 168 and 1440 h in a phosphate buffered solution at pH 7.4 with and without hydrogen peroxide were investigated. Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) was used to monitor the ion release into solution, X-ray Photoelectron Spectroscopy (XPS) was performed to unveil the chemistry of the leached surface, and High Resolution Transmission Electron Microscopy (HR-TEM) was carried out to monitor the structural modifications of the fibres. No significant differences were observed between dissolution experiments carried out with and without H2O2 with the exception of results after the first hour, from which it may be inferred that the dissolution proceeds faster in the presence of H2O2 but only in its very early steps. Congruent mobilization of Si and Mg from crocidolite was observed, increasing with time especially in the range between 1 and 48 h, while Ca decreased after 48 h and Fe was not detected at any incubation time. In the undersaturated conditions (0–48 h), dissolution rate of UICC crocidolite fibres has been estimated to be d(Si)/dt = 0.079 μmol h−1. The fibre surface modification is continuous with time: XPS results showed a regular depletion of Si and Mg and enrichment of Fe along dissolution. The Fe2p3/2 signal on the surface was fitted with four components at 709.0, 710.5, 711.6 and 712.8 eV binding energy values corresponding to: (i) Fe(II)–O and (ii) Fe(III)–O surrounded by oxygen atoms in the silicate structure, (iii) Fe(III)–OOH as a product of the dissolution process, and (iv) Fe in a phosphate precipitate (Fe–P), respectively. The evolution of Fe speciation on the crocidolite surface was followed by integrating the four photoemission peaks, and results showed that the oxidative environment promotes the formation of Fe(III)–O (up to 37% Fetot) and of Fe–P species (up to 16% Fetot), which are found on the fibre surface at the end of the dissolution experiment. HR-TEM showed that the crocidolite lattice structure, the fibrous habit and the high aspect ratio are preserved upon leaching, while Fe-bearing nanoparticles, likely amorphous and possibly displaced on top of the fibres, become clearly visible. As a conclusion, coating of the crocidolite fibres was demonstrated to occur due to precipitation of Fe-rich phases (both phosphates and oxide-hydroxides). The occurrence of such iron armouring may modulate asbestos toxicity and possibly be the initial step in the formation of asbestos ferruginous bodies.