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• New methods are requested for characterizing asbestos fibers in a mineral matrix. • SEM-Raman imaging is efficient for characterizing mineral fibers in-situ. • Confocal Raman imaging makes 3D analysis possible. • 3D analysis provides information on the aspect ratio and volume fraction of asbestos. • Fibers thinner than 400 nm can be identified by confocal Raman in SEM (λ = 532 nm). Asbestos consists in natural minerals crystallized in a specific habit and possessing in particular properties. In the case of Naturally Occurring Asbestos, usual methods applied to the identification of mineral fibers and the determination of their possible asbestiform nature seems not efficient, especially in the case of mineral fibers included in mineral matrix. We present a new in-situ method based on the use of confocal Raman-in-SEM imaging implemented in a Scanning Electron Microscope as an efficient method for in-situ mineralogy. The limitation of conventional methods is discussed. We applied 2D-Raman imaging to the identification of sub-micrometric fibers included in different mineral matrix. We were able to identify actinolite fibers down to 400 nm in diameter, included in feldspar, quartz and/or calcite matrix. Moreover, Confocal Raman allows the collection of 3D data that would provide access to critical information on the morphology of the amphibole fibers in the volume, such as aspect ratio, fibers distribution and amphibole volume fraction. We performed this method on various examples of rocks containing actinolite fibers of mean structural formula is: Na 0,04-0,12 Mg 2,79-3,73 Al 0,29-0,58 K 0,01 Ca 1,79-1,98 Mn 0,01-0,09 Fe2+ 0,99-1,91 Fe3+Si 7,64-7,73 O 22 (OH) 2. We demonstrated that coupling confocal Raman imaging and SEM is a new and efficient in-situ method for identification and morphological characterization of amphibole fibers. [ABSTRACT FROM AUTHOR]

Three fibrous amphiboles that are not regulated as asbestos-two from Biancavilla (Sicily, Italy) and one from Libby (MT, USA)-were studied in order to establish relationships between surface chemistry and surface reactivity. The three fibrous samples, plus one prismatic fluoro-edenite from Biancavilla that was used for comparison, were investigated by X-ray photoelectron spectroscopy (XPS) in order to obtain their quantitative surface compositions and to determine the chemical environment of the Fe in each case. In particular, the Fe 2p peak was fitted and, for the first for these materials, the binding energies of Fe(II) oxide, Fe(III) oxide and Fe(III) oxyhydroxide were identified. Bulk chemistries and Fe oxidation states were obtained from previous studies for the samples from Biancavilla, and were investigated in the present work by electron microprobe (EMP) and Fe Mössbauer spectroscopy (MS) for the sample from Libby. Comparison between surface and bulk data revealed that the sample with the lowest bulk Fe oxidation state was the one most affected by surface oxidation, while the samples with bulk highly-oxidised Fe were showing very high signal of Fe (III) oxy-hydroxide probably due to weathering. The surface reactivities of the fibrous amphiboles were investigated by measuring the production of the [DMPO, HO]• radical adduct using electron paramagnetic resonance (EPR) spectroscopy. Notably, significant chemical reactivity was observed; it was found to be comparable with-or, for the Libby sample, even higher than-that of fibrous tremolite (one of the six asbestos minerals). A positive linear correlation was observed when the production of HO• radical was plotted versus the Fe(II) content on the fibre surface. Data on fibrous tremolite obtained from previous studies were added to substantiate the correlation. These results provide evidence that Fe(II) at the fibre surface controls the production of radicals at the fibre surface. The observed relationship provides further confirmation that Fe topochemistry is strictly related to-though not solely responsible for-the toxicity of asbestos and other fibrous amphiboles that are not regulated as asbestos. [ABSTRACT FROM AUTHOR]

BACKGROUND. The inhalation of fibrous amphiboles can result in pulmonary fibrosis, lung cancer and mesothelioma. Although these fibres have the same disease-causing potential, their different morphologies and chemical composition can determine different biological activities. An unusual cluster of mesothelioma was evidenced in Biancavilla (Sicily) where no inhabitant had been significantly exposed to asbestos. OBJECTIVE. We herein discuss the mechanism of action of amphiboles, focusing on the fibres identified in the study area. RESULTS. Human lung carcinoma cells have been exposed to two different materials: prismatic fluoro-edenite and fibres with fluoro-edenitic composition. Only in the second case, they exhibit features typical of transformed cells, such as multinucleation, prosurvival activity and pro-inflammatory cytokine release. Accordingly, in vivo studies demonstrated that the fibrous sample only could induce a mesotheliomatogenic effect. Conclusions. Fibres with fluoro-edenitic composition behave similarly to the asbestos crocidolite, whose connection with inflammation and lung cancer is well established.