Reactive radicals at the surface of quartz or other SiO2 poly- morphs have been studied by EPR in relation to their possible role in pathogenicity. All the examined dusts bear the character- istic radicals of silica ground in air: Si, SiO, SiO2 (peroxyradi- cal) and O2 (superoxide ion), but some also show additional spectral lines belonging to other radical forms. Comparison of standard quartz dusts (DQ-12, Min-u-sil 5) with a natural quartz and with what obtained by grinding a very pure quartz crystal indicates that to a higher purity corresponds a higher rad- ical population. Cristobalite and vitreous silica exhibit similar spectra, with larger proportion by respect to quartz, of partially reduced oxygen forms. The reactivity of the silica surface to- wards O2 and NaClO aqueous solutions are investigated by ex- amining the modification in the EPR spectra induced by these treatments. A possible mechanism for fibrogenicity is proposed whereby, within the activated macrophage, a catalytic reaction occurs between surface functionalities and macrophage oxygen metabolites. This reaction would trigger the abnormal produc- tion of fibroblast stimulating factors, ending up with silicosis.
ADRIANF.J. (1968) Guideline for interpreting Electron Spin Resonance spectra of paramagnetic species adsorbed on surfaces. J. Coll. Interface Sci.26:317–354.
2.
ALLISONA.C., HARINGTONJ.S. and BIRBECKM. (1966) An explanation of the cytotoxic effects of silica on macrophages. J. Exp. Med.124:124–154.
3.
ANTONINIF. and HOCHSTRASSERG. (1972) Surface states of pristine silica surfaces. Surface Sci.32:644–664.
4.
BERESTETSKAYAV., BYSTRIKOVA.V., STRELETSKIJA.N. and BUTYAGINP. YU. (1980) Mechanochemistry of quartz surfaces. IV Interaction with oxygen. Kinetika i Kataliz21:1019–1022.
5.
BOLISV., FUBINIB. and VENTURELLOG. (1982) Phisico-chemical aspects on silicosis. Inorg. Chim. Acta. Bioinorg. Chem.79:302–303.
6.
BOLISV., FUBINIB. and VENTURELLOG. (1983) Surface characterization of various silicas. A tentative correlation between the energy of adsorption sites and the different biological activities. J. Thermal Anal.28:249–258.
7.
BYBERGJ.R., JENSENS.J.K. and MUUSL.T. (1967) ESR spectra from paramagnetic centers in irradiated KClO4. I The ClO2 center. J. Chem. Phys.46:131–137.
8.
BYERSP.D. and GAGEJ.C. (1961) The toxicity of precipitated silica. Brit. J. Industr. Med.18:295–302.
9.
CASTRANOVAV., VALLYATHANV., VAN DYKEK. and DALALN.S. (1989) Use of chemiluminescence assays to monitor the surface characteristics and biological reactivity on freshly fractured vs. aged silica. In “In Effect of Mineral Dusts on Cells”, MossmanB.T. and BeginR.O. eds., NATO ASI Series Vol. H 30, Springer-Verlag Berlin, 181–188.
10.
CHVAPILM. (1978) Old new problems of silicotic fibrosis. In “Biochemistry of Silicon and related problems”, BenzG. and LindqvistI. eds., Plenum Press, New York-London, 381.
11.
COOPEJ.A.R., GARDNERC.L., MCDOWELLC.A. and PELMANA.J. (1971) Electron spin resonance study of CIO2 and Cl2 adsorbed on zeolites. Mol. Phys.21:1043–1055.
12.
COSTAD. (1989) Propriété rédox de surface de poussières inorganiques en milieu aqueux. Relation avec leur proprietés cancérogènes et/ou fibrosantes. Thesis. Université P. et M. Curie, Paris.
13.
COSTAD., GUIGNARDJ., PEZERATH. and FUBINIB. (1990) Reactivité de surface des silices vis a vis de l'oxigène et de l'eau oxigénée dans la production de radicaux OH. Relations possibles avec la fibrogénèse. In “Les pneumopathies professionelles”SebastianP. ed. INSERM, Paris.
14.
CZERNIKOWSKIM. (1989) Etude physico-chimique des états de surface et de la passivation du quartz en relation avec son caractère pathogène. Thesis. Université d'Orleans. Orleans.
15.
DALALN.S., SHIX. and VALLYATHANV. (1989) Potential role of silicon-oxygen radicals in acute lung injury. In “Effect of mineral dusts on cells”MossmanB.T. and BeginR.O. eds, NATO ASI Series Vol H 30, Springer-Verlag, Berlin, 265–272. (1990) Role of the free radicals in the mechanisms of hemolysis and lipid peroxidation by silica: comparative ESR and cytotoxicity studies. J. Toxicol. Envir. Health 29:307–316.
16.
DAVISG.S. (1986) Pathogenesis of silicosis: current concept and hypothesis. Lung164:139–154.
17.
DEPASSEJ. and WARLUSJ. (1976) Relation between the toxicity of silica and its affinity for tetraalkylammonium groups. J. Colloid Interface Sci.56:618–621.
18.
DEPASSEJ. (1980) Mechanism of the haemolysis by colloidal silica. In “In vitro effects of Mineral dusts”BrownR.C., ChamberlainM. and DaviesR. (eds), Acad. Press, London, 125–130.
19.
ERRER. (1990) Caractérization des états de surface de quartz et des dépôts aluminignes en relation avec la silicose. In “Le pneumopathies professionelles”SebastienP. (ed) INSERM, Paris.
20.
FUBINIB., BOLISV. and GIAMELLOE. (1987 a) On the possible role of the silica surface chemistry in silicosis. In “Silicosis and mixed-dust pneumoconiosis”Le BouffantL. (ed), Colloque de l'INSERM155:115–122.
21.
FUBINIB., BOLISV. and GIAMELLOE. (1987 b) The surface chemistry of crushed quartz dusts is relation to its pathogenicity. Inorg. Chim. Acta, Bioinorg. Chem., 138:193–197.
22.
FUBINIB., GIAMELLOE., PUGLIESEL. and VOLANTEM. (1989 a) Mechanically induced defects in quartz and their impact on pathogenicity. Sol. State Ion.32-33:334–343.
23.
FUBINIB., BOLISV., GIAMELLOE., PUGLIESEL. and VOLANTEM. (1989 b) The formation of oxygen reactive radicals at the surface of the crushed quartz dusts as possible cause of silica pathogenicity. In “Effect on mineral dusts on cells”MossmanB.T. and BeginR.O. (eds), NATO ASI Series Vol H 30, Springer-Verlag, Berlin, 205–214.
24.
FUBINIB., GIAMELLOE. and VOLANTEM. (1989 c) the possible role of surface oxygen species in quartz pathogenicity. Inorg. Chim. Acta163:187–189.
25.
FUBINIB., BOLISV., GIAMELLOE., VOLANTEM. and COSTAD. (1990) Interaction between the surface of quartz and various substances mimicking the biological environment of the inhaled dust. In “Les pneumoconiosis professionelles”SebastienP. (ed) INSERM, Paris.
26.
GABORS. and ANCAZ. (1974) Effect of silica on lipid peroxidation in the red cells. Arch. Arbeitsmed.32:327–332.
27.
GABORS., ANCAZ. and ZUGRARUE. (1975) In vitro action of quartz on alveolar macrophage lipid peroxides. Arch. Environ. Health. 30:499–501.
28.
GIAMELLOE., FUBINIB., VOLANTEM. and COSTAD. (1990) Surface oxygen radicals originating via redox reactions during the mechanical activation of crystalline SiO2 in hydrogen peroxide. Colloids and surfaces, 45:155–165.
29.
GOLDSMITHD.F., WINND.M. and SHYC.M. (1986) Silica, silicosis and cancer. Controversy in occupational medecine. Praeger Publisher, New York.
30.
GOETHEC.J., LIDSTROML. and SWENSSONA. (1971) Influence of mode of disintegration on the fibrogenetic power of quartz particles. Med. Lav.62:375–377.
31.
GUIDOTTIT.L. and COHENB.H. (1986) Residence time and pulmonary response to inhaled SiO2 particles. In “Silica, silicosis and cancer”GoldsmithD.F., WinnD.M. and ShyC.M. (eds), Praeger Publisher, New York, 137–146.
32.
HALLIWELLB. and GUTTERIDGEJ.M.C. (1987) Free radicals in biology and medicine, Clarendon Press, Oxford, 257–260.
33.
HEMENWAYD.R., ABSHERM., LANDESMANM., TROMBLEYL. and EMERSONR.J. (1986) Differential lung response following silicon dioxide polymorph aerosol exposure. In “Silica, silicosis and cancer”GoldsmithD.F., WinnD.M. and ShyC.M. (eds), Praeger Publisher, New York, 105–116.
34.
HEPPLESTONA.G. and STYLESJ.A. (1967) Activity of a macrophage factor in collagen formation by Silica. Nature214:521–522.
35.
HEPPLESTONA.G. (1982) Silicotic fibrogenesis: a concept of pulmonary fibrogenesis. Ann. Occup. Hyg.26:449–462; (1984) Pulmonary toxicology of Silica, coal and asbestos. Envir. Health Persp. 55:111–127.
36.
HEPPLESTONA.G., KULONENE. and POTILAM. (1984) In vitro assessment of fibrosis of mineral dusts. Am. J. Ind. Med.6:373–386.
37.
HOBZAP., SAUERJ., MORGANEYERC., HURICHJ. and ZAHNADNIKR. (1981) Bonding ability of surface sites on silica and their effect on hydrogen bond. A quantum mechanic and statistical thermodynamic treatment. J. Phys. Chem.85:4061–4067.
38.
IARC monographs on the evaluation of the carcinogenic risk of chemicals to humans (1987) Silica and some silicates, 42:WHO, Lyon, France.
39.
ILERR.K. (1979) The chemistry of silica, John Wiley & Sons, New York.
40.
KILROE-SMITHT.A. (1974) Peroxidative action of quartz in relation to membrane. lysis-Environ. Res.7:110–116.
41.
KINGE.J., MOHANTYG.P., HARRISONC.V. and NAGELSCHMIDTG. (1953a) The action of different forms of pure silica on the lungs of rats. Brit. J. Ind. Med.10:(1953b) The action of flint of variable size injected at constant weight and constant surface into the lungs of rats. Brit. J. Ind. Med. 10:76–92.
42.
KLOSTERKÖTTERW. and ROBOCKK. (1975) New aspects on dusts and pneumoconiosis research. Am. Ind. Hyg. Ass. J., 659–668.
43.
KNÖZINGERH. (1976) Hydrogen bonds in systems of adsorbed molecules. In “The hydrogen bond”SchusterP., ZundelG. and SandorfyC. (eds), North Holland, Vol II1263–1359.
44.
KOLBANEVV., BERESTETSKAYAV. and BUTYAGINP. YU. (1980) Mechanochemistry of quartz surfaces. VI Properties of peroxide SiOOOSi. Kinetika i Kataliz21:1154–1158.
45.
KRIEGSEISW., BIEDERBICKR., BOESEJ., ROBOCKK. and SHARMANNA. (1977). Inhaled particles, Vol IV, Pergamon Press, Oxford, 345–357.
46.
LANGERA.M. (1978) Crystal faces and cleavage planes in quartz as templates in biological processes. Quart. Rev. Biophys.11:534–575. (1986) Cell type and response to siliceous minerals In “Silica Silicosis and Cancer”. Goldsmith D.F., Winn D.M. and Shy C.M. eds., Praegher publisher N.Y., 191–196.
47.
LANGERA.M. and NOLANR.P. (1986) Physicochemical properties of quartz controlling biological activity. In “Silica, silicosis and cancer”GoldsmithD.F., WinnD.M. and ShyC.M. (eds), Praeger Publisher, New York, 125.
48.
LE BOUFFANTL., DANIELH., MARTINJ.C. (1976) Therapeutic action of aluminium compounds on the development of experimental lesions produced by pure quartz or mixed dusts. In “Inhaled Particles and Vapours” vol. IV. WaltonW.A. ed, BOHS Edimburg London Pergamon Press389–401.
49.
MORROWB.A. and CODYL.A. (1976) Infrared studies of the reaction on oxide surfaces. 5 Lewis acid sites on dehydroxilated silica. J. Phys. Chem.80, 1995–1998.
50.
NASHT., ALLISONA.C. and HARINGTONJ.S. (1966) Physico-chemical properties of silica in relation to its toxicity. Nature210:259–261.
51.
NOLANR.P., LANGERA.M., HARINGTONJ.S., OSTERG, and SELIKOFFI.J. (1981) Quartz haemolysis as related to its surface functionalities. Environ. Res.26:503–520.
52.
PERNISB. and VIGLIANIE.C. (1982) The role of macrophages and immunocytes in the pathogenesis of pulmonary diseases due to mineral dusts. Am. J. Ind. Med.3:133–137.
53.
PEZERATH. (in press) Reactivité de surface des particules en relation avec leur proprietées en milieu biologique. In “Les pneumoconiosis professionelles”SebastienP. ed, INSERM, Paris.
54.
RAGHUNATHANP. and SURK. (1984) EPR study of the chloroperoxy radical CIOO, stabilized in the zeolitic host matrix of cancrinite. J. Am. Chem. Soc.106:8014–8017.
55.
RATDZIGV.A. and BYSTRIKOVA.V. (1978) ESR study of chemically active centers on the surface of quartz. Kinetika i Kataliz19:713–719.
56.
REISERK.M. and GERRIETSJ. (1986) Experimental silicosis mechanism of acute and chronic lung changes. In “Silica silicosis and cancer. Controversy in occupational medecine”GoldsmithD.F., WinnD.M. and ShyC.M. eds, Praeger Publisher, New York93–104.
57.
ROBOCKK. (1973) Standard quartz DQ 12 < 5 µm for experimental pneumoconiosis research project in the Federal Republic of Germany. Ann. Occup. Hyg.16:63–66.
58.
SAFFIOTTIV. (1986) The pathology induced by silica in relation to fibrogenesis and carcinogenesis. In “Silica silicosis and cancer. Controversy in occupational medecine”GoldsmithD.F., WinnD.M. and ShyC.M. eds, Praeger Publisher, New York, 287–307.
59.
SILICOSIS AND SILICATE DISEASE COMMITTEE (1988) Diseases associate with exposure to silica and nonfibrous silicate minerals. Arch. Pathol. Lab. Med. 112:673–720.
60.
STEINICKEU., HENNINGH.P., RICHTER-MENDAUJ. and KRETZCHMARU. (1982) Investigations of dissovling mechanically processed quartz grains. Crystal. Res. & Technol.17:1585–1590.
61.
STEINICKEU., KRETZSCHMARU., EBERTI. and HENNINGH.P. (1987) X-ray and spectroscopic studies of mechanically treated or irradiated oxides. Reactivity of Solids4:1–21.
62.
STRECKERF.J. (1965) Histophysiologische Untersuchungen zur silikotischen Gewebsreaktion im Intraperitonealtest und zurgewebswirkung von Coesit und Stischowit. Beitr. Silikose-Forsch. (Sbd.)6:55–83.
63.
SUMMERTONJ., HOENIGS., COOLEY BUTLERM. and CHVAPILM. (1977) The mechanism of haemolysis by silica and its bearing on silicosis. Exp. Mol. Path.26:123–128.
64.
UGLIENGOP., SAUNDERSV. and GARRONEE. (1990) Silanol as a model for the free hydroxyl of amorphous silica: ab initio calculations of the interaction with water. J. Phys. Chem.94:2260–2267.
65.
VALLYATHANV., SHIX., DALALN.S., IRRW. and CASTRANOVAV. (1988) Generation of free radicals from freshly fractured silica dust: potential role in acute silica-induced lung injury. Am. Rev. Respir. Dir.138:1213–1219.
66.
VILIMV., WILHELMJ., BRZÀKP. and HURICHJ. (1987) Stimulation of alveolar macrophages by mineral dusts in vitro: luminol-dependent chemiluminescence. Environ. Res.42:246–256.
67.
ZAV'YALOVS.A., STRELETSKIIA.N. and KARMANOVAE. (1985) Role of O2 radical anions in the formation and emission of molecules of singlet oxygen from a surface of freshly crushed quartz. Kinetika i Kataliz26:1005–1008.
