Nicola Bursi Gandolfi

Assessment of asbestos body formation by high resolution FEG-SEM after exposure of Sprague-Dawley rats to chrysotile, crocidolite, or erionite.

This work presents a comparative FEG-SEM study of the morphological and chemical characteristics of both asbestos bodies and fibres found in the tissues of Sprague-Dawley rats subjected to intraperitoneal or intrapleural injection of UICC chrysotile, UICC crocidolite and erionite from Jersey, Nevada (USA), with monitoring up to 3 years after exposure. Due to unequal dosing based on number of fibres per mass for chrysotile with respect to crocidolite and erionite, excessive fibre burden and fibre aggregation during injection that especially for chrysotile would likely not represent what humans would be exposed to, caution must be taken in extrapolating our results based on instillation in experimental animals to human inhalation. Notwithstanding, the results of this study may help to better understand the mechanism of formation of asbestos bodies. For chrysotile and crocidolite, asbestos bodies are systematically formed on long asbestos fibres. The number of coated fibres is only 3.3% in chrysotile inoculated tissues. In UICC crocidolite, Mg, Si, and Fe are associated with the fibres whereas Fe, P and Ca are associated with the coating. Even for crocidolite, most of the observed fibres are uncoated as coated fibres are about 5.7%. Asbestos bodies do not form on erionite fibres. The crystal habit, crystallinity and chemistry of all fibre species do not change with contact time, with the exception of chrysotile which shows signs of leaching of Mg. A model for the formation of asbestos bodies from mineral fibres is postulated. Because the three fibre species show limited signs of dissolution in the tissue, they cannot act as source of elements (primarily Fe, P and Ca) promoting nucleation and growth of asbestos bodies. Hence, the limited number of coated fibres should be due to the lack of nutrients or organic nature.

Determination of the concentration of asbestos minerals in highly contaminated mine tailings: An example from abandoned mine waste of Crètaz and Èmarese (Valle d’Aosta, Italy)

Abstract For the first time, this work reports concentration maps of asbestos minerals in contaminated mine tailings drawn using the results of Rietveld quantitative phase analysis (QPA). The investigated sites are located in the Valle d’Aosta region (Italy): Crètaz, the most important Italian magnetite mine, active until 1979 and Emarèse, one the most important chrysotile asbestos mines in Italy, active until 1968. The results of the study permit to draw the spatial distribution of the asbestos (chrysotile and tremolite in this specific case) concentration, useful to plan reclamation of the sites, with priority given to the areas with the highest asbestos concentration. Because of the complexity of the mineral assemblage, which includes, among the others, antigorite, chlorite, talc, and tremolite, the concentration of chrysotile was cross-checked using different experimental techniques such as X-ray powder diffraction (XRPD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), polarized light optical microscopy (PCOM), and differential thermal analysis (DTA). The accuracy of the results was validated by analyzing standard samples with known concentrations of chrysotile and tremolite. The comparison allowed to point out the advantages and disadvantages of each experimental method. At Crètaz, chrysotile ranges from 4.4 to 22.8 wt% and tremolite from 1.0 to 10.3 wt%, whereas at Emarèse the concentration of chrysotile varies from 3.3 to 39.5 wt% and tremolite from 5.9 to 12.4 wt%. Antigorite and chlorite are the major accompanying phases with variable amounts of other accessory minerals including magnetite, carbonates, talc, olivine, pyroxene, talc, and brucite. The results of our study are of key importance for the local environmental policies as the knowledge of the spatial distribution of the asbestos concentration allows to plan a detailed reclamation agenda of the contaminated sites. The spots with the highest surface contamination of both chrysotile and tremolite were identified and classified as priority areas in the reclamation plan.

Where is iron in erionite? A multidisciplinary study on fibrous erionite-Na from Jersey (Nevada, USA)

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.

New insights into the toxicity of mineral fibres: A combined in situ synchrotron μ-XRD and HR-TEM study of chrysotile, crocidolite, and erionite fibres found in the tissues of Sprague-Dawley rats

Along the line of the recent research topic aimed at understanding the in vivo activity of mineral fibres and their mechanisms of toxicity, this work describes the morpho-chemical characteristics of the mineral fibres found in the tissues of Sprague-Dawley rats subjected to intraperitoneal/intrapleural injection of UICC chrysotile, UICC crocidolite and erionite-Na from Nevada (USA). The fibres are studied with in situ synchrotron powder diffraction and high resolution transmission electron microscopy to improve our understanding of the mechanisms of toxicity of these mineral fibres. In contact with the tissues of the rats, chrysotile fibres are prone to dissolve, with leaching of Mg and production of a silica rich relict. On the other hand, crocidolite and erionite-Na fibres are stable even for very long contact times within the tissues of the rats, showing just a thin dissolution amorphous halo. These findings support the model of a lower biopersistence of chrysotile with respect to crocidolite and erionite-Na but the formation of a silica-rich fibrous residue after the pseudo-amorphization of chrysotile may justify a higher cytotoxic potential and intense inflammatory activity of chrysotile in the short term in contact with the lung tissues.

The crystal structure of mineral fibres: 1. Chrysotile

This work reports the result s of the structural study of three representative chrysotile samples of different provenance (Canadian UICC, and Italian Balangero and Valmalenco) . Chemical composition was determined using EMPA and TG data. An innovative wet cryo-milling procedure was used to powder the resistant-to-abrasion chrysotile fibres. X-ray powder diffraction patterns were collected using both conventional and non-conventional sources. Collected data were used for Rietveld structural refinements and results were compared with available literature data. The three samples display similar structure models, although small differences were detected in the position of the oxygen atoms. Both the structural refinements and spectroscopic investigations confirms that Fe 2+ and Fe 3+ atoms in chrysotile are located in the octahedral cavities only, substituting for Mg 2+ . Regarding the atom coordinates, UICC chrysotile is the more similar to the model reported by Falini et al. (2004). About the lattice parameters, the Valmalenco chrysotile is the more similar, if compared with the Balangero and UICC, to both the model proposed by Whittaker (1956a,b) and Falini et al. (2004) . This work is intended as a basis for subsequent studies aimed at understanding the potential toxicity of these mineral fibres.

The crystal structure of mineral fibres: 2. Amosite and fibrous anthophyllite

This study reports for the first time crystal-structure data for amosite and fibrous anthophyllite. The chemical composition of the two fibre species was determined from EMPA. Crystal structures were refined using powder-diffraction data, using both laboratory sources and synchrotron radiation. Results were compared with the available literature data for the non-fibrous varieties grunerite and anthophyllite, respectively. The calculated site-occupancies for all samples are in agreement with the chemical compositions calculated from EMPA. The existing structure models of grunerite and orthorhombic anthophyllite also applies to the corresponding fibrous varieties amosite and fibrous anthophyllite, respectively. In amosite, both Fe2+ and Fe3+ atoms are found at the sites M(1), M(2) and M(3) and Fe2+ ions is the only atomic species found at site M(4). Mg is disordered over the C sites with a preference for site M(2). Minor Ca and Na have been assigned to the A site. In fibrous anthophyllite, Mg is the only atomic species found at the M1, M2 and M3 sites. Fe2+, Mg (and minor Mn) have been assigned to the M4 site, whereas minor Ca has been assigned to the A site. In both structures, the environment at the M(4) site in amosite and M4 site is in fibrous anthophyllite highly distorted. This work can be considered a basis for studies aimed at understanding the potential toxicity/pathogenicity of these mineral fibres.

In vitro acellular dissolution of mineral fibres: A comparative study

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.

Is fibrous ferrierite a potential health hazard? Characterization and comparison with fibrous erionite

Abstract Fibrous erionite is classified by the International Agency for Research on Cancer (IARC) as carcinogenic substance to humans (Group 1). In the areas where it is present in the bedrock, it may cause environmental exposure, and both professional and environmental exposures are possible when the bedrock is used for industrial applications (e.g., building materials). For health and environment protection, prevention is a priority action. In this framework, the recent guidelines of the Consensus Report of the Weinman International Conference on Mesothelioma suggest identifying locations where potentially hazardous mineral fibers (like erionite) are found in the environment, to prevent environmental exposure. The present study will show that one such potentially hazardous mineral fiber might be fibrous ferrierite. Here, the mineralogy, chemical-physical properties, and surface activity of a hydrothermal fibrous ferrierite from Monte Lake British Columbia (Canada) and a diagenetic fibrous ferrierite from Lovelock, Nevada (U.S.A.), were investigated using a combination of “state of the art” experimental methods including optical microscopy, electron microscopy and microprobe analysis, laser ablation-inductively coupled plasma-mass spectrometry (for the trace elements), vibrational spectroscopy, electron paramagnetic resonance, and synchrotron powder diffraction. The chemical-physical properties of these fibrous ferrierites (morphometric parameters, specific surface area, chemical composition with special attention to metals, mainly iron) that prompted adverse effects in vivo were compared to those of the positive carcinogenic standard fibrous erionite-Na from Jersey, Nevada (U.S.A.). The results of our study have demonstrated that, although there are differences in the crystal chemistry and genetic environment, ferrierite samples exhibit outstanding similarities with fibrous erionite samples: both fibrous erionite and fibrous ferrierite may occur in large amounts as microcrystalline fibrous–asbestiform phases in diagenetic rocks with fibers of breathable sizes. For both zeolites, iron is not structural but is associated with impurities lying at the surface of the fibers. Moreover, data useful to understand the surface activity of these fibrous ferrierites were collected. As far as hydrothermal sample is concerned, the EPR data indicate the presence of hydrophilic (SiO-, AlO-, SiOH) and hydrophobic (Si-O-Si) interacting surface groups able to bind the charged CAT1 probes at close sites and attract the probes in the water pools formed into the fiber aggregates. A high percentage of CAT1 probes weakly interacting with the surface due to competition with metal ions were observed for surface of the diagenetic sample. CAT8 probes were less adsorbed by its surface if compared to the diagenetic sample but the more charged surface provided a stronger binding strength for the diagenetic sample compared to the hydrothermal one. In summary, the results of this study indicate that fibrous ferrierite may represent a potential health hazard and, applying the precautionary principle, it should undergo a procedure of toxicity testing.