ESR Spin Trapping and Cytotoxicity Investigations of Freshly Fractured Quartz: Mechanism of Acute Silicosis

"Electron spin resonance (ESR) measurements show that grinding of quartz particles in air produces silicon-based (Si- and SiO-) radicals which decay with aging in air. ESR spin trapping measurements provide evidence for the generation of hydroxyl and possibly superoxide radicals from a suspension of fresh quartz particles. The hydroxyl radical generation potential of the fresh quartz particles decreases on storing in ambient air and on the addition of catalase, superoxide dismutase, desferoxamine, or DMSO. Silica-induced lipid peroxidation also decreases on storing the fresh particles in ambient air. These findings suggest that oxygenated radicals play a role in the biochemical mechanism of pneumoconiosis in general and acute silicosis in particular.INTRODUCTIONThis communication summarizes our electron spin resonance (ESR) investigation of the formation of oxygenated radicals by freshly crushed quartz particles in a cell-free aqueous medium, and its potential role in the biochemical mechanism of acute silicosis. This study was undertaken because the mechanisms by which the quartz particles exert their toxic action on cells and the process(es) by which these actions progress to fibrogenesis are still not well understood. 1-3 It is generally believed, however, that the action of quartz particles on the cell membrane is the starting point of the silicotic process. 1,4 Since the first step must involve surface reactions, characterization of the chemical structure of the surface of quartz particles has been the subject of several recent studies!-' For example, we reported that mechanical crushing of quartz under normal atmosphere generates silicon-based (Si• and SiO•) radicals which decay with time, and that these radicals are associated with a higher cytotoxicity of fresh quartz dust as compared to that of an aged dust from the same stock. 6,8 Independently Fubini and coworkers' have also reported on the formation of Si• and SiO• -type of radicals from quartz particles crushed under atmospheric conditions. Gulumian and van Wyk9 have reported that quartz particles react with hydrogen peroxide (H202) to generate hydroxyl (•OH) radicals. These authors9 suggested that this process might contribute to quartz's pathogenicity but the mechanism of the -OH radical formation was not clarified. Earlier, Gabor and Anca10 had suggested that the cytotoxicity of quartz particles might be associated with the generation of some factor or factors possessing the properties of a free radical and hence capable of promoting the peroxidative chain cleavage of polyunsaturated fatty acid moieties of the phospholipids in the cell membrane. More recently, Weitzman and Graceffa 11 reported that asbestos is able to catalyze the generation of -OH radicals from H2O2. Their later work12 indicated that lipid peroxidation might be one of the mechanisms of tissue injury by asbestos."