The mechanism through which asbestos amphiboles may give rise to mesothelioma is still not completely understood. Several factors have been taken into account, and these include the morphological aspect of the fiber, the chemical composition, and a variety of surface properties which are ultimately responsible for the mineral-cellule interactions[1]. Studies in vitro demonstrate that the morphology of the fiber has a strong role in determining its biological danger, because very thin and long crystallites are hardly eliminated by the alveolar macrophages. However, recent studied show that lung injury after asbestos exposure is associated with an oxidative stress that is catalyzed by iron in the fiber[2]. It follows that the rapid determination of the chemical composition of asbestiform amphiboles, and of its Mg/Fe ratio in particular, is extremely important in environmental studies. The direct analysis can be achieved only by micro-chemical tools such as by EDS- or WDS-equipped electron microscopes. However, these techniques are extremely expensive and often unsuitable when dealing with extremely fibrous (diameter < 3 µm) materials. Therefore a rapid and easily accessible method is highly desirable in large scale environmental monitoring. The best alternative to EMPA is provided by FTIR spectroscopy, a technique which can be used on both single crystals (down to few µm in dimension) and powders. Here we present the results of a new calibration based on the analysis of a large set of well-characterized fibrous and prismatic natural amphiboles spanning a very large variety of chemical compositions and geological occurrences. All samples were previously studied using X-ray diffraction and EMPA. FTIR spectra in the principal OH-stretching region were collected on KBr disks prepared with a mineral:matrix = 5:150 mg ratio. Most spectra show four prominent bands which can be assigned to the combination of Mg and F2+ at the OH-coordinated M(1,3) sites[3,4,5,6]. The digitized spectra were fitted by interactive optimization followed by least-squares refinement; all bands were modelled as symmetric Gaussians. [3,4] showed that the binary site-occupancies at M(1) and M(3) in the amphibole structure are related to the observed intensities of the four (A to D) components in the principal IR OH-stretching spectrum. Using the original equations of [7]: M(1,3)Mg = 3IA + 2IB + IC and M(1,3)M2+ = IB + 2IC + 3ID (with M2+ = Fe2+) where IA-ID are the intensities measured for the corresponding A to D bands, one can derive the (Mg, M2+) site populations at M(1,3) with a high degree of confidence. This method is particularly suitable for asbestiform materials which cannot be properly characterized by EMP. The present work shows that the above spectroscopic tool can be applied to a large variety of amphibole types. For species were significant (Mg, Fe) are present at M(4) (i.e. anthophyllite–cummingtonite–grunerite) an additional information (e.g. Mössbauer) is however required for a complete characterization of the sample. [1] van Oss, C.J., Naim, J.O., Costanza, P.M., Giese, R.F. Jr., Wu, W., Sorling, A.F. (1999) Clays and Clay Minerals, 47, 697-707. [2] Xinchao, W., Wu, Y., Stonehuerner, J.G., Dailey, L.A., Richards, J.D., Jaspers, I., Piantadosi, C.A., Ghio, A.J. (2006) Am. J. Respir. Cell. Mol. Biol., 34, 286–292. [3] Della Ventura, G., Robert, J.-L., Hawthorne, F.C. (1996) Geochimica and Cosmochimica Acta, vol. spec. 5, 55-63. [4] Della Ventura, G., Robert, J.-L., Raudsepp, M., Hawthorne, F.C., Welch, M. (1997) American Mineralogist, 82, 291-301. [5] Iezzi, G., Della Ventura, G., Hawthorne, F.C., Pedrazzi, G., Robert, J.-L., Novembre, D. (2005) European Journal of Mineralogy, 17, 733-740. [6] Iezzi, G., Della Ventura, G., Bellatreccia, F., Lo Mastro, S., Gunther, M., Bandly, (2007) Mineralogical Magazine, in press. [7] Burns, R.G. and Strens, R.G.J. (1966) Science, 153, 890-892.

DELLA VENTURA, G., Bellatreccia, F., Iezzi, G., Redhammer, G., Zelli, F., Pezzo, G.T.D. (2007). Crystal-chemical characterization of fibrous amphiboles by FTIR and Mössbauer spectroscopies, 15-16.

Crystal-chemical characterization of fibrous amphiboles by FTIR and Mössbauer spectroscopies

DELLA VENTURA, Giancarlo;BELLATRECCIA, FABIO;
2007-01-01

Abstract

The mechanism through which asbestos amphiboles may give rise to mesothelioma is still not completely understood. Several factors have been taken into account, and these include the morphological aspect of the fiber, the chemical composition, and a variety of surface properties which are ultimately responsible for the mineral-cellule interactions[1]. Studies in vitro demonstrate that the morphology of the fiber has a strong role in determining its biological danger, because very thin and long crystallites are hardly eliminated by the alveolar macrophages. However, recent studied show that lung injury after asbestos exposure is associated with an oxidative stress that is catalyzed by iron in the fiber[2]. It follows that the rapid determination of the chemical composition of asbestiform amphiboles, and of its Mg/Fe ratio in particular, is extremely important in environmental studies. The direct analysis can be achieved only by micro-chemical tools such as by EDS- or WDS-equipped electron microscopes. However, these techniques are extremely expensive and often unsuitable when dealing with extremely fibrous (diameter < 3 µm) materials. Therefore a rapid and easily accessible method is highly desirable in large scale environmental monitoring. The best alternative to EMPA is provided by FTIR spectroscopy, a technique which can be used on both single crystals (down to few µm in dimension) and powders. Here we present the results of a new calibration based on the analysis of a large set of well-characterized fibrous and prismatic natural amphiboles spanning a very large variety of chemical compositions and geological occurrences. All samples were previously studied using X-ray diffraction and EMPA. FTIR spectra in the principal OH-stretching region were collected on KBr disks prepared with a mineral:matrix = 5:150 mg ratio. Most spectra show four prominent bands which can be assigned to the combination of Mg and F2+ at the OH-coordinated M(1,3) sites[3,4,5,6]. The digitized spectra were fitted by interactive optimization followed by least-squares refinement; all bands were modelled as symmetric Gaussians. [3,4] showed that the binary site-occupancies at M(1) and M(3) in the amphibole structure are related to the observed intensities of the four (A to D) components in the principal IR OH-stretching spectrum. Using the original equations of [7]: M(1,3)Mg = 3IA + 2IB + IC and M(1,3)M2+ = IB + 2IC + 3ID (with M2+ = Fe2+) where IA-ID are the intensities measured for the corresponding A to D bands, one can derive the (Mg, M2+) site populations at M(1,3) with a high degree of confidence. This method is particularly suitable for asbestiform materials which cannot be properly characterized by EMP. The present work shows that the above spectroscopic tool can be applied to a large variety of amphibole types. For species were significant (Mg, Fe) are present at M(4) (i.e. anthophyllite–cummingtonite–grunerite) an additional information (e.g. Mössbauer) is however required for a complete characterization of the sample. [1] van Oss, C.J., Naim, J.O., Costanza, P.M., Giese, R.F. Jr., Wu, W., Sorling, A.F. (1999) Clays and Clay Minerals, 47, 697-707. [2] Xinchao, W., Wu, Y., Stonehuerner, J.G., Dailey, L.A., Richards, J.D., Jaspers, I., Piantadosi, C.A., Ghio, A.J. (2006) Am. J. Respir. Cell. Mol. Biol., 34, 286–292. [3] Della Ventura, G., Robert, J.-L., Hawthorne, F.C. (1996) Geochimica and Cosmochimica Acta, vol. spec. 5, 55-63. [4] Della Ventura, G., Robert, J.-L., Raudsepp, M., Hawthorne, F.C., Welch, M. (1997) American Mineralogist, 82, 291-301. [5] Iezzi, G., Della Ventura, G., Hawthorne, F.C., Pedrazzi, G., Robert, J.-L., Novembre, D. (2005) European Journal of Mineralogy, 17, 733-740. [6] Iezzi, G., Della Ventura, G., Bellatreccia, F., Lo Mastro, S., Gunther, M., Bandly, (2007) Mineralogical Magazine, in press. [7] Burns, R.G. and Strens, R.G.J. (1966) Science, 153, 890-892.
2007
DELLA VENTURA, G., Bellatreccia, F., Iezzi, G., Redhammer, G., Zelli, F., Pezzo, G.T.D. (2007). Crystal-chemical characterization of fibrous amphiboles by FTIR and Mössbauer spectroscopies, 15-16.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11590/174846
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