Surface and Bulk IR Modes of Crystalline and Amorphous Silica: A Study of the Relation of Surface Structure to Cytotoxicity of Respirable Silica

"Surface IR (infrared) modes of crystalline and fumed (amorphous) silica particles, calcined at temperatures up to 1095°C, have been studied by Fourier transform infrared spectroscopy. The ability of these same particles to lyse cells has been measured by a hemolysis protocol. The untreated crystalline and amorphous materials differ by a factor of 40 in specific surface area, and the intensity per unit mass of the sharp surface silanol band near 3745 cm-1 in the amorphous material is an order of magnitude larger than in the crystalline material. A similar difference is observed in the lysing potential of the two materials. The intensity of the silanol band increases after calcination for both materials, reaching peak values near 500°C, followed by a dramatic drop at higher calcination temperatures, and reaching negligible values for materials calcined near 1100°C. The lysing potential data follow essentially the same pattern for both crystalline and fumed silica. These results are consistent with the hypothesis that the surface silanol groups are involved in cell lysis. Further experiments are suggested to evaluate the relationship between the surface structure of ailica particles and their potential cytotoxicity. IntroductionThe characterization of the surface structure of various allotropic forms of silica is of interest because the cytotoxicity of silica particles of respirable size has been commonly related to the chemical interaction of functional groups on the surface of such particles with the lipoproteins contained in cell membranes (1-3). It has been found that the cytotoxic potential of silica particles varies greatly with their crystalline structure (4,5), particle size (6-8), surface composition (9), and molecular surface configuration (1,10). Studies of the infrared (IR) modes of various forms of silica have been reported by a number of researchers (3 ,11-19). Several books and reviews (20-24) have dealt with the identification of functional groups on silica surfaces and the effect of heat treatment on the surface structure. The nature of the surface is said to be critical in determining the biological activity of silica dusts (3).Fourier transform infrared (FTIR) spectroscopy is a highly sensitive ·technique for identifying IR surface modes of tine particulates, and it was deemed of interest to examine the surface structure and its relation to lysing potential of two widely different types of respirable silica dust. The lysing potential of respirable dust particles has been considered a first-level test for potential cytotoxicity."