The mechanisms underlying asbestos toxicity mainly rely on experiments performed on “laboratory” fibers, but little data is available on naturally occurring asbestos (NOA). Human exposure to NOA is subject to their ecopersistence and the modulation of their potential toxicity following weathering. The effect of weathering on three fibrous minerals from the Italian Western Alps, chrysotile, tremolite, and balangeroite—a Fe-rich asbestiform mineral—was investigated by mimicking more than 100 yr of physical (freezing–thawing/wetting–drying cycles in a climatic chamber) and biochemical forces (incubation with oxalic acid). Ion release, evaluated by means of inductively coupled plasma–atomic emission spectroscopy (ICP-AES), and variation in chemical composition, evaluated by scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), indicated that weathering modified the fibers in the series: chrysotile > balangeroite > tremolite. Kinetics of ion release from the fibers (Mg, Fe, and Si) revealed different ion removal pathways. Tremolite was poorly affected. Chrysotile preferentially released cations up to a plateau, with physical and biochemical forces acting competitively. Conversely, for balangeroite, upon which weathering forces acted synergistically, the initial loss of ions facilitated further dissolution and more Si than Mg was released, suggesting an ongoing collapse of the crystal structure. Depletion of redox-reactive ions produced a significant reduction in fiber-derived •OH radicals (EPR, spin-trapping technique), but the fibrous nature was always retained. Despite weathered fibers appearing less toxic than “stored/laboratory” ones, NOA is to be considered far from safe because of fibrous nature and residual surface reactivity. Risk assessment needs to consider the effect of weathering on exposures. Both tremolite and balangeroite may contaminate, in some areas, chrysotile asbestos. However, in contrast to tremolite, balangeroite exhibits a low ecopersistence, similar to chrysotile behavior. Any contribution of balangeroite to chrysotile toxicity will thus be related to its quantitative occurrence and not to higher structural stability.
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