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The environmental impact of natural occurrences of asbestos (NOA) and asbestos-like minerals is a growing concern for environmental protection agencies. The lack of shared sampling and analytical procedures hinders effectively addressing this issue. To investigate the hazard posed by NOA, a multidisciplinary approach that encompasses geology, mineralogy, chemistry, and toxicology is proposed and demonstrated here, on a natural occurrence of antigorite from a site in Varenna Valley, Italy. Antigorite is, together with chrysotile asbestos, one of the serpentine polymorphs and its toxicological profile is still under debate. We described field and petrographic analyses required to sample a vein and to evaluate the NOA-hazard. A combination of standardized mechanical stress and automated morphometrical analyses on milled samples allowed to quantify the asbestos-like morphology. The low congruent solubility in acidic simulated body fluid, together with the toxicity-relevant surface reactivity due to iron speciation, signalled a bio-activity similar or even greater to that of chrysotile. Structural information on the genetic mechanism of antigorite asbestos-like fibres in nature were provided. Overall, the NOA site was reported to contain veins of asbestos-like antigorite and should be regarded as source of potentially toxic fibres during hazard assessment procedure., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Exposure to asbestos and asbestos-like minerals has been related to the development of severe lung diseases, including cancer and malignant mesothelioma (MM). A high incidence of non-occupational MM was observed in New Caledonia (France) in people living in proximity of serpentinite outcrops, containing chrysotile and fibrous antigorite. Antigorite is a magnesium silicate, which shares with chrysotile asbestos the chemical formula. To achieve information on antigorite toxicity, we investigated the physico-minero-chemical features relevant for toxicity and cellular effects elicited on murine macrophages (MH-S) and alveolar epithelial cells (A549) of three fibrous antigorites (f-Atg) collected in a Caledonian nickel lateritic ore and subjected to supergene alteration. Field Atg were milled to obtain samples suitable for toxicological studies with a similar particle size distribution. UICC chrysotile (Ctl) and a non-fibrous antigorite (nf-Atg) were used as reference minerals. A high variability in toxicity was observed depending on shape, chemical alteration, and surface reactivity. The antigorites shared with Ctl a similar surface area (16.3, 12.1, 20.3, 13.4, and 15.6 m 2 /g for f-Atg1, 2, 3, nf-Atg, and Ctl). f-Atg showed different level of pedogenetic weathering (Ni depletion f-Atg1 ≪ f-Atg2 and 3) and contained about 50% of elongated mineral particles, some of which exhibited high aspect ratios (AR > 10 μm, 20%, 26%, 31% for f-Atg1, 2, and 3, respectively). The minerals differed in bio-accessible iron at pH 4.5 (f-Atg1 ≪ f-Atg3, < f-Atg2, nf-Atg < Ctl), and surface reactivity (ROS release in solution, f-Atg1 ≪ f-Atg2, 3, nf-Atg, and Ctl). f-Atg2 and f-Atg3 induced oxidative stress and pro-inflammatory responses, while the less altered, poorly reactive sample (f-Atg1) induced negligible effects, as well nf-Atg. The slow dissolution kinetics observed in simulated body fluids may signal a high biopersistence. Overall, our work revealed a significative cellular toxicity of f-Atg that correlates with fibrous habit and surface reactivity., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

In Naturally Occurring Asbestos (NOA) rich areas, water flows through asbestos bearing rocks and soils and generates waterborne fibres that may migrate in air and become a risk for humans. Research on the migration and dispersion after water vaporisation has been so far only marginally evaluated. This study investigates the migration in air of asbestos from a set of suspensions contaminated by chrysotile from Balangero (Italy), under controlled laboratory conditions. We evaluated i) the morphological modifications that might occur to chrysotile during migration from water to air, and ii) the amount of airborne chrysotile mobilised from standardised suspensions. Morphological alteration of asbestos fibres occurred during water-air migration and impacted on the analytical response of electron microscopy. Waterborne asbestos concentration higher than 40 ∙ 10 6 f/L generates in air concentration higher than 1 fibre per litre [f/L], the alarm threshold limit set by World Health Organization for airborne asbestos. A possible correlation between the waterborne fibre concentration as mass or number of fibres per volume unit [μg/L or f/L] was observed., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

This study discloses the morphological and chemical-structural modifications that occur during thermal degradation of amphibole asbestos. Low-iron tremolite and iron-rich crocidolite were heated at temperatures ranging from r.t. to 1200 °C. Heating promoted a complex sequence of iron oxidation, migration and/or clustering and, finally, the formation of brittle fibrous pseudomorphs consisting of newly formed minerals and amorphous nanophases. The effects of the thermal modifications on toxicologically relevant asbestos reactivity were evaluated by quantifying carbon- and oxygen-centred, namely hydroxyl (OH), radicals. Heating did not alter carbon radicals, but largely affected oxygen-centred radical yields. At low temperature, reactivity of both amphiboles decreased. At 1200 °C, tremolite structural breakdown was achieved and the reactivity was further reduced by migration of reactive iron ions into the more stable TO 4 tetrahedra of the newly formed pyroxene(s). Differently, crocidolite breakdown at 1000 °C induced the formation of hematite, Fe-rich pyroxene, cristobalite, and abundant amorphous material and restored radical reactivity. Our finding suggests that thermally treated asbestos and its breakdown products still share some toxicologically relevant properties with pristine fibre. Asbestos inertization studies should consider morphology and surface reactivity, beyond crystallinity, when proving that a thermally inactivated asbestos-containing material is safe., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Among the physico-chemical features responsible for the so-called "variability of quartz hazard", a key role has been assigned to the silica surface charge, evaluated by means of ζ potential measurement. The ζ potential of silica describes the protonation state of silanols which, in turn, determine interactions with cell membranes. To gain a molecular understanding of the role of silanols in silica pathogenicity, we conducted a systematic investigation of the variation of the ζ potential as a function of pH (ζ plot titration curve) on a large set of respirable quartz particles with different levels of metal contaminants. The membranolytic activity of the particles on red blood cells, used as a readout of pathogenic activity, was assessed in parallel. Pure quartz surfaces showed sigmoid-shaped ζ plots suggesting the presence of silanol families with similar acidity, whereas contaminated dusts exhibited convex-shaped ζ plots, indicating a higher silanol heterogeneity on contaminated surfaces with respect to the pure ones. The quartz particles with a higher surface heterogeneity related to metal contamination showed a higher membranolytic activity. By removing structural defects and chemical heterogeneity, the ζ plot shifted towards the typical shape of pure quartz and the membranolytic activity was reduced. We conclude that the ζ plot is a useful readout to measure the acid-base behavior of quartz surfaces and to describe the chemical heterogeneity of quartz silanols. Surface heterogeneity, here induced by metal contamination, is proposed as the main cause of quartz membranolytic activity, further supporting the hypothesis that surface silanol disorganization determines silica pathogenicity., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Magnetite-containing glass-ceramics are promising bio-materials for replacing bone tissue after tumour resection. Thanks to their ferrimagnetic properties, they generate heat when subjected to an alternated magnetic field. In virtue of this they can be employed for the hyperthermic treatment of cancer. Moreover, grafting anti-cancer drugs onto their surface produces specific anti-neoplastic activity in these biomaterials. Gallic acid (GA) exhibits antiproliferative activity which renders it a promising candidate for anticancer applications. In the present paper, the reactivity of ferrimagnetic glass-ceramic SC-45 grafted with GA (SC-45+GA) was studied in terms of ROS release, rupture of the C-H bond of the formate molecule and Fenton reactivity by EPR/spin trapping in acellular systems. The ability of these materials to cause lipid peroxidation was assessed by UV-vis/TBA assay employing linoleic acid as a model of membrane lipid. The results, compared to those obtained with SC-45, showed that GA grafting (i) significantly enhanced the Fenton reactivity and (ii) restored the former reactivity of SC-45 towards both the C-H bond and linoleic acid which had been completely suppressed by prolonged contact with water. Fe 2+ centres at the surface are probably implicated. GA, acting as a pro-oxidant, reduces Fe 3+ to Fe 2+ by maintaining a supply of Fe 2+ at the surface of SC-45+GA., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Industrial processing of materials containing quartz induces physico-chemical modifications that contribute to the variability of quartz hazard in different plants. Here, modifications affecting a quartz-rich sand during cast iron production, have been investigated. Composition, morphology, presence of radicals associated to quartz and reactivity in free radical generation were studied on a raw sand and on a dust recovered after mould dismantling. Additionally, cytotoxicity of the processed dust and ROS and NO generation were evaluated on MH-S macrophages. Particle morphology and size were marginally affected by casting processing, which caused only a slight increase of the amount of respirable fraction. The raw sand was able to catalyze OH and CO2(-) generation in cell-free test, even if in a lesser extent than the reference quartz (Min-U-Sil), and shows hAl radicals, conventionally found in any quartz-bearing raw materials. Enrichment in iron and extensive coverage with amorphous carbon were observed during processing. They likely contributed, respectively, to increasing the ability of processed dust to release CO2- and to suppressing OH generation respect to the raw sand. Carbon coverage and repeated thermal treatments during industrial processing also caused annealing of radiogenic hAl defects. Finally, no cellular responses were observed with the respirable fraction of the processed powder., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The natural occurrence of asbestos (NOA) in rural areas is a serious concern for human health and the dispersion route of asbestos in the proximity of natural asbestos-rich settings has been marginally evaluated so far. NOA may affect air, but also water and soil quality. In rural areas population may be exposed to asbestos with a largely unknown impact on human health. This work investigates the potential exposure of a farmer cultivating a field nearby the largest former asbestos mine of Western Europe (Balangero, Italy). The concentration of waterborne asbestos in the stream used to water the field was measured (ca. 2×10(5) fibers per liter, ff/L) and the cultivated ultramafic topsoil characterized, evidencing a remarkable occurrence of chrysotile. The worker's personal exposure and the environmental fiber dispersion during a simulated agricultural activity (tillage) were quantified in two independent trials. During the trials, the worker was exposed to average concentrations of 16 and 26 ff/L, with a peak of 40 ff/L. These data inform about the possible exposure of an agricultural worker to asbestos concentration higher than the accepted threshold of 2 ff/L. The release of asbestos fibers into the environment was negligible (0-2 ff/L)., (Copyright © 2016 Elsevier B.V. All rights reserved.)