Fibrous Ferrierite from Northern Italy: Mineralogical Characterization, Surface Properties, and Assessment of Potential Toxicity

Abstract

Nowadays, fibrous minerals pose as significant health hazards to humans, and exposure to these fibers can lead to the development of severe pulmonary diseases. This work investigated the morphology, crystal structure, chemistry, and surface activity of fibrous ferrierite recently found in northern Italy through an integrated approach using scanning electron microscopy–energy dispersive spectroscopy, electron microprobe, inductively coupled plasma atomic emission spectrometry, X-ray powder diffraction, and electron paramagnetic resonance. Our results show that a notable amount of ferrierite fibers are breathable (average length ~22 µm, average diameter 0.9 µm, diameter-length ratio >> 1:3) and able to reach the alveolar space (average Dae value 2.5 μm). The prevailing extra-framework cations are in the Mg > (Ca ≈ K) relationship, R is from 0.81 to 0.83, and the Si/Al ratio is high (4.2–4.8). The <T-O> bond distances suggest the occurrence of some degree of Si,Al ordering, with Al showing a site-specific occupation preference T1 > T2 > T3 > T4. Ferrierite fibers show high amounts of adsorbed EPR probes, suggesting a high ability to adsorb and interact with related chemicals. According to these results, fibrous ferrierite can be considered a potential health hazard, and a precautionary approach should be applied when this material is handled. Future in vitro and in vivo tests are necessary to provide further experimental confirmation of the outcome of this work.

Another Potentially Hazardous Zeolite from Northern Italy: Fibrous Mordenite

“…Basalt vesicles are often filled with secondary minerals of hydrothermal origin, especially zeolites (analcime, chabazite, phillipsite, harmotome, gmelinite, yugawaralite, and willhendersonite [16][17][18][19]). Moreover, other fibrous zeolites (erionite, offretite, and ferrierite) have been recently discovered in several localities of Lessini Mounts: these findings are of particular importance due to their toxicological implications [20][21][22][23][24]. Furthermore, in the Dolomites area (where Fassa Valley is located), a great amount of volcanic material is present.…”

“…Mordenite resulted not mutagenic and the presence of ferrous ion in the crystals did not alter mordenite's mutagenic potential [43]. Many other fibrous zeolites such as erionite [48][49][50], offretite [23,51], ferrierite [24,52,53], mesolite, and thomsonite [54] resulted in different toxicity and carcinogenicity response to humans.…”

The in vitro cytotoxic effects of natural (fibrous epsomite crystals) and synthetic (Epsom salt) magnesium sulfate

“…Some mineral fibers such as asbestos (chrysotile, amosite, crocidolite, asbestos anthophyllite, asbestos tremolite and asbestos actinolite) and zeolites, in particular erionite, have been extensively investigated in the last decades (e.g., Cangiotti et al, 2017, 2018; Gualtieri, 2023; World Health Organization, 1986; Thompson et al, 2017; Mirata et al, 2022) and classified as a carcinogen for humans (class 1) by International Agency for Research on Cancer (IARC, 2012). For other minerals such as ferrierite (Gualtieri, 2018; Mattioli et al, 2022; Zoboli et al, 2019), mordenite (Di Giuseppe, 2020; Giordani, Ballirano, et al, 2022), offretite (Giordani et al, 2019; Mattioli et al, 2018), scolecite (Mattioli et al, 2016), mesolite and thomsonite (Betti et al, 2022; Giordani, Mattioli, et al, 2022), and others (e.g., fluoro‐edenite, winchite, richterite, clay minerals; Gianfagna et al, 2003; NIOSH, 2011; Erskine & Bailey, 2018; Larson et al, 2016), the current knowledge does not permit an accurate risk classification. Exposure to mineral fibers represents a serious environmental hazard strictly correlated to fibrotic pulmonary diseases, pneumoconiosis, and various types of cancer in exposed subjects (Aust et al, 2011; Di Giuseppe et al, 2021; Gualtieri et al, 2017).…”