The study of the mechanisms by which mineral fibres promote adverse effects in both animals and humans is a hot topic of multidisciplinary research with many aspects that still need to be elucidated. Besides length and diameter, a key parameter that determines the toxicity/pathogenicity of a fibre is biopersistence, one component of which is biodurability. In this paper, biodurability of mineral fibres of social and economic importance (chrysotile, amphibole asbestos and fibrous erionite) has been determined for the first time in a systematic comparative way from in vitro acellular dissolution experiments. Dissolution was possible using the Gamble solution as simulated lung fluid (pH = 4 and at body temperature) so to reproduce the macrophage phagolysosome environment. The investigated mineral fibres display very different dissolution rates. For a 0.25 μm thick fibre, the calculated dissolution time of chrysotile is in the range 94–177 days, very short if compared to that of amphibole fibres (49–245 years), and fibrous erionite (181 years). Diffraction and SEM data on the dissolution products evidence that chrysotile rapidly undergoes amorphization with the formation of a nanophasic silica-rich fibrous metastable pseudomorph as first dissolution step whereas amphibole asbestos and fibrous erionite show minor signs of dissolution even after 9–12 months.
For the first time, this paper reports a systematic and comparative study of the thermal behaviour of fibres of social, health, economic and industrial relevance using thermogravimetric and differential scanning calorimetry (TG/DSC). The mineral fibres selected for the study are: three chrysotiles samples, crocidolite, tremolite asbestos, amosite, anthophyllite asbestos and fibrous erionite.Powder X-ray diffraction (PXRD) and scanning electron microscopy combined with energy dispersive spectrometry (SEM/EDS) were used for the characterization of the mineral fibres before and after heating at 1000 or 1100 °C to identify the products of the thermal decomposition at a microscopic and structural scale and characterize their thermal behaviour.TG/DSC data allowed the determination of the structural water content and temperature stability.Furthermore thermal analysis provided a sensitive and reliable technique for the detection of small quantities of different mineral phases occurring as impurities. After thermal treatment, fibrous samples were completely transformed into various iron oxide, cristobalite and other silicate phases which preserved the original overall fibrous morphology (as pseudomorphosis). Only crocidolite at 1100 °C was partially melted and an amorphous surface was observed.
Fibrous erionite is a mineral fibre of great concern but to date mechanisms by which it induces cyto- and geno-toxic damage, and especially the role of iron associated to this zeolite species, remain poorly understood. One of the reasons is that we still don’t know exactly where iron is in natural erionite. This work is focused on fibrous erionite-Na from Jersey (Nevada, USA) and attempts to draw a general model of occurrence of iron in erionite and relationship with toxicity mechanisms. It was found that iron is present as 6-fold coordinated Fe3+ not part of the zeolite structure. The heterogeneous nature of the sample was revealed as receptacle of different iron-bearing impurities (amorphous iron-rich nanoparticles, micro-particles of iron oxides/hydroxides, and flakes of nontronite). If iron is not part of the structure, its role should be considered irrelevant for erionite toxicity, and other factors like biopersistence should be invoked. An alternative perspective to the proposed model is that iron rich nano-particles and nontronite dissolve in the intracellular acidic environment, leaving a residue of iron atoms at specific surface sites anchored to the windows of the zeolite channels. These sites may be active later as low nuclearity groups.
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