Alessandro Cavallo

The zeta potential of mineral fibres

For the first time, the zeta (ξ) potential of pathogenic mineral fibres (chrysotiles, amphiboles and erionite) was systematically investigated to shed light on the relationship between surface reactivity and fibre pathogenicity. A general model explaining the zeta potential of chrysotile, amphiboles and erionite has been postulated. In double distilled water, chrysotiles showed positive values while crocidolite and erionite showed negative values. In contact with organic solutions, all fibres exhibited negative values of zeta potential. The decrease of the surface potential is deemed to be a defensive chemical response of the macrophage cells to minimize hemolytic damage. Negatively charged surfaces favour the binding of collagen and redox activated Fe-rich proteins, to form the so-called asbestos bodies and prompt the formation of HO via the reaction with peroxide (H2O2+e(-)→HO+HO(-)). An additional mechanism accounting for higher carcinogenicity is possibly related to the Ca(2+) sequestration by the fibres with surface negative potential, impairing the mitochondrial apoptotic pathway. It was also found that with a negative zeta potential, the attractive forces prevailed over repulsions and favoured processes such as agglomeration responsible of a tumorigenic chronic inflammation.

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.

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.

Ornamental stones of the Verbano Cusio Ossola quarry district: characterization of materials, quarrying techniques and history and relevance to local and national heritage

Abstract This paper reports the results of an Interreg Project (OSMATER – Sub-Alpine Observatory Materials Territory Restoration) that investigated the present and historical quarrying and processing activities in the cross-border area between the Ossola Valley (Italy) and the Canton Ticino (Switzerland), and the use of dimension stones in local and national architecture. These materials are in many ways unique for their abundance and lithological variety. In the past, their extraction, processing and application characterized in a decisive way the architectural and constructive culture, both in terms of prestigious architecture and civil buildings, establishing a relationship between ‘stones and culture’, and ‘territory and its resources’. In recent years, many traditions of the quarrying, processing and architectural activities are losing importance and interest is being loss, resulting in a loss of knowledge and historical memory. The loss of this knowledge is likely to become irreversible in the short term, with the disappearance of people and social groups as depositaries of tradition. We conclude that the creation of an ‘observatory’, like OSMATER, is desirable and, indeed, essential if we want to preserve the historical memory of the stone industry of an entire production area.

The effect of Alpine metamorphism on an oceanic Cu-Fe sulfide ore: the Herin deposit, Western Alps, Italy

Herin mine (Champdepraz, Aosta, Italy), located in Aosta Valley, approximately between 1600 and 1800 m a.s.l., was exploited for at least 250 years for its Cu-Fe sulfide ore. The deposit host rocks belong to the metaophiolitic Zermatt-Saas unit, the eclogitic lower portion of the Piedmont Western Alpine Nappe. The ore mineral association mainly comprises pyrite and chalcopyrite, along with other sulfides such as pyrrhotite, sphalerite, cubanite and oxides (magnetite, rutile, ilmenite). The deposit consists in lenticular massive bodies and thin layers hosted in various greenschist-facies metamorphosed lithotypes. New data on geometric features, mineralogy, mineral chemistry, petrography, minerography were collected and compared with the existing models for massive-sulfide mineral deposits. We suggest a hydrothermal-volcanogenic primary origin of the mineralization with primary characters largely obliterated by subsequent metamorphic history. On the basis of previous works and our results, we identified two parameters as driving criteria for a comprehension of the multistage process that led to the present configuration of the ore: (a) textural characters of pyrite and (b) distribution of selected trace elements (Co, Ni, As) in sulfides. Spot analyses and atomic maps obtained by electron microprobe provided an integration of these two sets of data. Trace elements, in fact, show a zoned distribution, in particular in pyrite, that can be related to specific textural styles. We selected Co as a useful trace element, due to its high concentration and wide range in pyrite (270-22200 ppm). Besides we determined a critical concentration value for cobalt of 3160 ppm, as discriminating between two generations of pyrite. This led to outline a series of dissolution and crystallization events, that describes the metamorphic history of the sulfide ore.

Granites of the Verbano-Cusio-Ossola District (Piedmont, Northern Italy): Possible Candidates for the Designation of “Global Heritage Stone Province” and a Proposal of a Geotouristic Route

The Verbano-Cusio-Ossola quarrying district (Piedmont, northern Italy) produces many different ornamental stones, one of the most important represented by “granite”, available in different colours and textures (e.g. “Rosa Baveno” and “Bianco Montorfano”). These late-Variscan granites crop out in the southern Verbano area, and their extraction dates back at least to the XV century. The diffusion of these granites is on a global scale, but there are excellent examples of local and regional use in churches and buildings. The quarrying and processing techniques have evolved and specialized over time, leading to the development of highly skilled workers. Currently the quarrying activity is somewhat reduced. However the area is an excellent example both for the recovery of waste materials and for the immense historical and artistic heritage, the result of hundreds of years of activity. Over 5 centuries of quarrying and building activities have left an important historical and artistic legacy, which could be the subject of geotouristic routes. In order to reach this goal, a greater sensibility is needed towards the historical and cultural significance of the stones (knowledge of the geological, petrographical, physical—mechanical data of the different materials).