Geochemistry International

, Volume 56, Issue 7, pp 617–627 | Cite as

Experimental Study of Unequilibrated Silica Transfer from Liquid Water to the Vapor Phase

  • V. A. AlekseyevEmail author
  • L. S. Medvedeva
  • V. N. Balashov
  • A. A. Burmistrov
  • I. N. Gromyak


Experiments were carried out in hermetically sealed platinum capsules, with water saturated with silica with respect to quartz at 300°C in the lower parts of the electric furnaces, where the temperature slightly increases upward at 0.15°C/cm. Our earlier studies (Alekseyev and Medvedeva, 2017) have shown that these exactly experimental parameters are favorable for silica transfer from the liquid to vapor phase. The statistically processed experimental results show that the molal silica concentration in the liquid phase (m) exponentially decreases with time. This dependence and the fact that the newly produced opal occurs on the capsule walls above the meniscus are consistent with the distillation model. The scatter of the experimental m values turned out to be caused not by differences in the temperature gradient in different wells of the electric furnaces but by the natural roughness of the inner walls of the capsules, which differed from one capsule to another and could even change with time in any given capsule. In the capsules with roughness artificially made on their walls, m decreased much more rapidly, and not only in the bottom but also in the upper parts of the electric furnaces, where temperature decreased upward (–0.08°C/cm). This may suggest that the discovered phenomenon is spread in nature more widely than surmised previously, because this phenomenon does not strongly depend on the direction of the temperature gradient, and voids in natural rocks usually have rough walls.


quartz water temperature gradient equilibrium disturbance distillation roughness opal quartz veins 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. A. W. Adamson and A. P. Gast, Physical Chemistry of Surfaces. 6th ed., (John Wiley & Sons, New York, 1997).Google Scholar
  2. V. A. Alekseyev and L. S. Medvedeva, “Silica distribution in the system quartz–water–vapor depending on the temperature gradient,” Geochem. Int. 56 (2), 136–147 (2018).CrossRefGoogle Scholar
  3. V. A. Alekseyev, V. M. Balashov, and G. P. Zaraisky, “Kinetics and modeling of fluid–rock interactions,” Petrology 5, 37–44 (1997).Google Scholar
  4. V. A. Alekseyev, L. S. Medvedeva, L. N. Kochnova, and O. A. Tytyunnik, “Mechanisms of silica precipitation from hydrothermal solutions: The effects of solution evaporations and quartz seed crystals,” Geochem. Int. 48 (2) 178–182 (2010).CrossRefGoogle Scholar
  5. V. A. Alexeyev, L. S. Medvedeva, and N. P. Starshinova, “Paradoxical transformation of the equilibrium quartz–water system into an unequilibrated one,” Geochem. Int. 51(5), 382–404 (2013).CrossRefGoogle Scholar
  6. J. Bico, C. Tordeux, and D. Quéré, “Rough wetting,” Europhys. Lett. 55, 214–220 (2001).CrossRefGoogle Scholar
  7. J. Bico, U. Thiele, and D. Quéré, “Wetting of textured surfaces,” Colloids and Surfaces A 206, 41–46 (2002).CrossRefGoogle Scholar
  8. C. Buffone and K. Sefiane, “IR measurements of interfacial temperature during phase change in a confined environment,” Experimental Thermal and Fluid Science 29, 65–74 (2004).CrossRefGoogle Scholar
  9. C. Buffone, K. Sefiane, and C. Minetti, “The effect of wall thickness and material on Marangoni driven convection in capillaries,” Colloids and Surfaces A 481, 384–392 (2015).CrossRefGoogle Scholar
  10. J. S. Cline, R. J. Bodnar, and J. D. Rimstidt, “Numerical simulation of fluid flow and silica transport and deposition in boiling hydrothermal solutions: application to epithermal gold deposits,” J. Geophys. Res. 97, 9085–9103 (1992).CrossRefGoogle Scholar
  11. D. A. Crerar and G. M. Anderson, “Solubility and solvation reactions of quartz in dilute hydrothermal solutions,” Chem. Geol. 8, 107–122 (1971).CrossRefGoogle Scholar
  12. J. D. Dana, E. S. Dana, and C. Frondel, The System of Mineralogy. V. 3. Silica Minerals. (John Wiley and Sons, New York, 1962).Google Scholar
  13. P. J. Darragh, A. J. Gaskin, B. C. Terrell, and J. V. Sanders, “Origin of precious opal,” Nature 209 (5018), 13–16 (1966).CrossRefGoogle Scholar
  14. D. J. DeMaster, “The diagenesis of biogenic silica: chemical transformations occurring in the water column, seabed, and crust,” in Treatise on Geochemistry V. 7, Ed. by. H. D. Holland and K. K. Turekian, (Elsevier, 2003), pp. 87–98.CrossRefGoogle Scholar
  15. P. M. Dove, “Kinetic and thermodynamic controls on silica reactivity in weathering environments,” Rev. Mineral. 31, 235–290 (1995).Google Scholar
  16. L. R. Drees, L. P. Wilding, N. E. Smeck, and A. L. Senkayi, “Silica in soils: Quartz and disordered silica polymorphs,” in Minerals in Soil Environments, Ed. by J. B. Dixon and S. B. Weed, (Soil Sci. Soc. Am., Madison, 1989), pp. 913–974.Google Scholar
  17. S. E. Drummond and H. Ohmoto, “Chemical evolution and mineral deposition in boiling hydrothermal systems,” Econ. Geol. 80, 126–147 (1985).CrossRefGoogle Scholar
  18. O. W. Flörke, H. Graetsch, B. Martin, K. Röller, and R. Wirth, “Nomenclature of micro– and non–crystalline silica minerals, based on structure and microstructure,” Neues Jahrbuch Miner. Abh. 163, 19–42 (1991).Google Scholar
  19. R. O. Fournier, and R. W. Potter, “An equation correlating the solubility of quartz in water from 25° to 900°C at pressures up to 10000 bars,” Geochim. Cosmochim. Acta 46, 1969–1973 (1982).CrossRefGoogle Scholar
  20. R. M. Gel’man, and I. Z. Starobina, Photometric Methods of Determination of Rock–Forming Elements in Ores, Rocks, and Minerals (Min. Geologii RSFSR, Leningrad, 1970) [in Russian].Google Scholar
  21. I. Gunnarsson and S. Arnórsson, “Amorphous silica solubility and the thermodynamic properties of H4SiO°4 in the range of 0° to 350°C at Psat,” Geochim. Cosmochim. Acta 64, 2295–2307 (2000).CrossRefGoogle Scholar
  22. K. M. Hay and M. I. Dragila, “Physics of fluid spreading on rough surfaces.,” Int. J. Numerical Analysis 5, 85–92 (2008).Google Scholar
  23. K. M. Hay, M. I. Dragila, and J. Liburdy, “Theoretical model for the wetting of a rough surface,” J. Colloids Interface Sci. 325, 472–477 (2008).CrossRefGoogle Scholar
  24. J. J. Hemley, J. W. Montoya, J. W. Marinenko, and R. W. Luce, “Equilibria in the system Al2O3–SiO2–H2O and some general implications for alteration/mineralization processes,” Econ. Geol. 75, 210–228 (1980).CrossRefGoogle Scholar
  25. N. R. Herdianita, P. R. L. Browne, K. A. Rodgers, and K. A. Campbell, “Mineralogical and textural changes accompanying ageing of silica sinter,” Mineral. Deposita 35, 48–62 (2000).CrossRefGoogle Scholar
  26. M. Hosaka and S. Taki, “Hydrothermal growth of quartz crystals at low fillings in NaCl and KCl solutions,” J. Cryst. Growth 78, 413–417 (1986).CrossRefGoogle Scholar
  27. K. Hoshino, T. Itami, R. Shiokawa, and M. Watanabe, “A possible role of boiling in ore deposition: A numerical approach,” Resource Geol. 56, 49–54 (2006).CrossRefGoogle Scholar
  28. M. Hovland, H. G. Rueslåtten, H. K. Johnsen, B. Kvamme, and T. Kuznetsova, “Salt formation associated with sub–surface boiling and supercritical water,” Marine Petrol. Geol. 23, 855–869 (2006).CrossRefGoogle Scholar
  29. R. K. Iler, “Formation of precious opal,” Nature 207 (4996). 472–473 (1965).CrossRefGoogle Scholar
  30. G. C. Kennedy, “A portion of the system silica–water,” Econ. Geol. 45, 629–653 (1950).CrossRefGoogle Scholar
  31. I. N. Kigai and B. R. Tagirov, “Evolution of acidity of hydrothermal fluids related to hydrolysis of chlorides,” Petrology 18, 252–262 (2010).CrossRefGoogle Scholar
  32. S. Kitahara, “The solubility of quartz in water at high temperatures and high pressures,” Rev. Phys. Chem. Jpn. 30, 109–114 (1960).Google Scholar
  33. D. London and G. B. Morgan VI,“The pegmatite puzzle,” Elements 8, 263–268 (2012).CrossRefGoogle Scholar
  34. E. Merino and Y. Wang, “Self–organization in rocks: occurrences, observations, modeling, testing––with emphasis on agate genesis,” in Non–Equilibrium Processes and Dissipative Structures in Geoscience V. 11, Ed. by H.–J. Krug and J. H. Kruhl, Yearbook “Self–Organization” (Duncker & Humblot, Berlin, 2001), pp. 13–45.Google Scholar
  35. P. Ortoleva, J. Chadam, E. Merino, and A. Sen, “Geochemical self–organization II; the reactive–infiltration instability,” Am. J. Sci. 287, 1008–1040 (1987).CrossRefGoogle Scholar
  36. S. S. Panchamgam, A. Chatterjee, J. L. Plawsky, and P. C. Wayner, Jr., “Comprehensive experimental and theoretical study of fluid flow and heat transfer in a microscopic evaporating meniscus in a miniature heat exchanger,” Int. J. Heat Mass Transfer. 51, 5368–5379 (2008).CrossRefGoogle Scholar
  37. B. Pewkliang, A. Pring, and J. Brugger, “The formation of precious opal: clues from the opalization of bone,” Can. Mineral. 46, 139–149 (2008).CrossRefGoogle Scholar
  38. J. L. Plawsky, M. Ojha, A. Chatterjee, and P. C. Wayner Jr., “Review of the effects of surface topography, surface chemistry, and fluid physics on evaporation at the contact line,” Chem. Engin. Commun. 196, 658–696 (2008).CrossRefGoogle Scholar
  39. A. V. Plyasunov, “Thermodynamics of Si(OH)4 in the vapor phase of water: Henry’s and vapor–liquid distribution constants, fugacity and cross virial coefficients,” Geochim. Cosmochim. Acta 77, 215–231 (2012).CrossRefGoogle Scholar
  40. R. A. Pollock, G. Yu. Gor, B. R. Walsh, J. Fry, I. T. Ghampson, Yu. B. Melnichenko, H. Kaiser, W. J. DeSisto, M. C. Wheeler, and B. G. Frederick, “Role of liquid vs vapor water in the hydrothermal degradation of SBA–15,” J. Phys. Chem. C 116, 22802–22814 (2012).CrossRefGoogle Scholar
  41. D. Quéré, “Rough ideas on wetting,” Physica A 313, 32–46 (2002).CrossRefGoogle Scholar
  42. J. D. Rimstidt and H. L. Barnes, “The kinetics of silica–water reactions,” Geochim. Cosmochim. Acta 44, 1683–1699 (1980).CrossRefGoogle Scholar
  43. Y. Shibue, “Empirical expressions of quartz solubility in H2O, H2O + CO2, and H2O + NaCl fluids,” Geochem. J. 30, 339–354 (1996).CrossRefGoogle Scholar
  44. C. H. Sondergeld and D. L. Turcotte, “A laboratory study of mineral deposition in a boiling environment,” Econ. Geol. 74, 109–115 (1979).CrossRefGoogle Scholar
  45. C. I. Steefel and A. C. Lasaga, “A coupled model for transport of multiple chemical species and kinetic precipitation/ dissolution reactions with application to reactive flow in single phase hydrothermal systems,” Am. J. Sci. 294 (5), 529–592 (1994).CrossRefGoogle Scholar
  46. M. P. Verma, “Chemical thermodynamics of silica: a critique on its geothermometer,” Geothermics 29, 323–346 (2000).CrossRefGoogle Scholar
  47. Y. Wang and E. Merino, “Self–organization origin of agates: Banding, fiber twisting, composition, and dynamic crystallization model,” Geochim. Cosmochim. Acta 54, 1627–1638 (1990).CrossRefGoogle Scholar
  48. M. Wangen and I. A. Munz, “Formation of quartz veins by local dissolution and transport of silica,” Chem. Geol. 209, 179–192 (2004).CrossRefGoogle Scholar
  49. G. P. Zaraiskii, “The conditions of the nonequilibrium silicification of rocks and quartz vein formation during acidic metasomatism,” Geol. Ore Deposits 41, (4), 262–275 (1999).Google Scholar

Copyright information

© Pleiades Publishing, Ltd. 2018

Authors and Affiliations

  • V. A. Alekseyev
    • 1
    Email author
  • L. S. Medvedeva
    • 1
  • V. N. Balashov
    • 2
  • A. A. Burmistrov
    • 1
  • I. N. Gromyak
    • 1
  1. 1.Vernadsky Institute of Geochemistry and Analytical Chemistry (GEOKhI)Russian Academy of SciencesMoscowRussia
  2. 2.Earth and Environmental Systems InstitutePennsylvania State UniversityState CollegeUnited States

Personalised recommendations