Silica in hot-spring waters

Abstract The silica in hot-spring waters and in a few cold waters was studied by moans of the colorimetrie ammonium-molybdate method of analysis. Murata found in 1947 that only a part of the total silica in aged samples of high-silica waters was determinable by the colorimetric method. Weitz , franck And schuchard later showed that ammonium molybdate reacts readily with the monomeric form of silica (probably H4SiO4) but very slowly with polymeric silica. If the colorimetric measurement is completed in two or three minutes, only the monomer is determined. Nearly all silica of hot springs is in the monomeric form. Solubility equilibrium exists between dissolved (monomeric) and amorphous silica. For the hot springs that were studied, the solubility is about 315 p.p.m. at 90°C and 110 p.p.m. at 25°C, which is very similar to Krauskopf's experimental data. Monomeric silica polymerizes so slowly to colloidal silica that many waters are supersaturated with respect to amorphous silica. The rate of polymerization is influenced by pH, temperature, degree of supersaturation, presence of previously formed colloidal and gelatinous silica and contact with opal and other substances. Supersaturated acid waters and alkaline waters with less than 100% supersaturation tend to remain supersaturated almost indefinitely, with little or no change. Precipitation of colloidal silica is favoured by high temperature and contact with opal. Many connate and other ground waters, including some thermal springs, are much below saturation with respect to amorphous silica, probably because low-solubility quartz and chalcedony have been precipitating. Quartz is favoured by relatively high temperature, slow rale of precipitation, and low degree of supersaturation, and is believed to form by deposition of monomeric molecules. Chalcedony is probably deposited when the degree of supersaturation is moderately high and the rate of deposition is relatively fast. The ranges of temperature over which quartz and chalcedony deposit no doubt overlap, but, if other factors are equal, quartz is favoured by high temperature. Opal is favoured by relatively low temperature and rapid rate of precipitation. Although opal has probably been deposited at temperatures as high as 140°C, it is unstable and is slowly converted to chalcedony or quartz. Water that is saturated with respect to opal is highly supersaturated with respect to quartz. Opal is probably formed from monomeric or more probably, the smaller polymeric molecules of silica, retaining some of their water content. Evidence is lacking for the direct conversion of gelatinous silica to opal. Some differences in solubility probably exist between amorphous opal and opal that shows X-ray patterns like that of cristobalite. The suggestion is made that clay minerals form by combination of monomeric silica and a comparable form of monomeric alumina, which must have very low solubility in waters within the pH range of 5 to 9. Because of the abundance and relatively high solubility of silica, the proposed reaction, dissolved alumina + dissolved silica ⇌ clay, is ordinarily displaced strongly to the right in hydrothermal alteration and in ordinary soil formation. With removal of free silica, aided by tropical rainfall and temperatures, the reaction may be displaced to the left by dissolution and removal of silica from the system. Alumina, because of its very low solubility, remains as bauxite.