ESR Evidence for the Hydroxyl Radical Formation in Aqueous Suspension of Quartz Particles and Its Possible Significance to Lipid Peroxidation in Silicosis

"Electron spin resonance (ESRJ spectrum of the hydroxyl (· OH) radical spin adduct with .the spin trap 5,5-dimethyl-1-pyrrolintt-N-oxide has been obtained in suspensions of freshly ground quartz particles. The concentration of the spin adduct (and hence of the • OH radicals) increases with the amount of grinding. The dust's potential for the generation of the· OH radicals is maximum when fresh (i.e., immediately after grinding) and decreases to 50% in about a day on storage in air. Studies involving metal chelates .indicate that the • OH radical formation involves mainly the silica surface and H20 rather than the Fenton reaction. The results suggest that hydroxyl radical reaction(s) could be important in the lipid peroxidation and fibrogenicity by quartz dust, particularly .in acute silicosis. INTRODUCTIONIn this paper we report on our electron spin resonance (ESR) detection of the formation of hydroxyl (·OH) radicals in aqueous suspensions of freshly crushed quartz particles. This work was undertaken with a view to find possible clues to the role of free radicals in the pathogenesis of quartz-induced fibrogenicity, commonly known as silicosis. We noted that while silicosis is one of the major health hazards in coal and mineral industries, the mechanism by which the quartz particles exert their toxic action on cells and the process(es) by which these actions progress to fibrogenesis are still poorly ·understood (Reiser and Last, 1979; Singh and .Rahman, 1987). It is generally thought, nevertheless, that the action of quartz particles on the biological membranes is the starting point of the silicotic process (Parazzi et - al., 1968). A possible clue to the mechanism of the membrane damage by quartz particles, in terms of the role of oxygenated free radicals, is suggested by the following observations. A suspension of quartz particles in contact with alveolar macrophages has been reported (Gabor et al., 1975; Koike et al., 1982) to initiate an enhancement of lipid peroxidation, defined broadly as the oxidative deterioration of polyunsaturated components of lipids. Hydroxyl (· OH) radicals are known to be capable of peroxidation by abstracting hydrogen atoms from cell-membrane lipids (Halliwell and Gutteridge, 1985) and of initiating lipid peroxidation in lysosomal membranes. (Fong et al., 1973). Arong other lines, it is known that exposure of cell membranes, fatty acids, and unsaturated food oils to ionizing radiation, which generates· OH radicals, causes rapid peroxidation (Halliwell and Gutteridge, 1985). Thus • OH radicals (and also other oxygenated species such as Oi, 10 2, and H20 2) might be expected to play a role in the toxicity of quartz. Earlier studies of the aqueous chemistry of quartz suspensions have reported detection of H2O 2 (Kalbanev et al., 1980), implicating the formation of ·OH radicals as transient species. However, we are not aware of any report of the detection of • OH radicals in quartz reactions, and thus the present study was undertaken. Since it-is known that, because of their high reactivity (hence short lifetime) in aqueous media, the • OH radicals cannot be detected via ESR directly (Finkelstein et al., 1980; Buettner, 1982) we have used .ESR combined with the spin-trap methodology (Finkelstein et al., 1980) for studying the· OH formation. The results show that· OH radicals are indeed formed in aqueous suspensions of freshly ground quartz; thus pointing to ·a possible new clue to the cytotoxicity of freshly formed quartz particles and thereby to silica fibrogenicity."