Ukrainian Antarctic journal

No 1(18) (2019): Ukrainian Antarctic Journal

Adsorption properties of the fumed individual and mixed Si, Ti and Al oxides as proxies for the Antarctic atmospheric mineral aerosols

M. S. Bazylevska
Institute of Geological Sciences, National Academy of Sciences of Ukraine, 55B O. Gonchara Str., Kyiv, 01054, Ukraine
V. I. Bogillo
Institute of Geological Sciences, National Academy of Sciences of Ukraine, 55B O. Gonchara Str., Kyiv, 01054, Ukraine
Published December 13, 2019
  • mineral aerosols,
  • Antarctic atmosphere,
  • fumed individual and mixed Si, Ti and Al oxides,
  • nitrogen adsorption


The aim of the study is to determine the effects of structure and content of X, CX in the oxides X/SiO2 (X = Al2O3, TiO2, Al2O3/TiO2) on the surface characteristics. The low-temperature nitrogen adsorption isotherms on the surface of 12 individual and mixed fumed oxides of Si, Ti and Al, as proxies for the Antarctic  atmospheric mineral aerosols, were measured by volumetric method. The specific surface areas of the oxides, SBET were calculated by using the Brunauer–Emmett–Teller (BET) theory. The dependence between CX and SBET is not obeyed for the mixed oxides, which can be caused by effects of the reaction temperature of MCln (M = Si, Ti and Al) hydrolysis in the oxygen/hydrogen flame and by different concentration ratios of O2, H2 and MCln on the structural characteristics of the primary particles and their aggregates. The N2 adsorption energy distributions of the oxides surface were calculated by the regularization procedure. It was demonstrated that the surfaces are characterized by high energetic heterogeneity. Result. The Zero-Adsorption Isotherm (ZAI) approach was applied to describe the N2 adsorption in the whole range of its pressures. The ZAI derived in approximation of adsorbed vapor as a set of molecular clusters. The specific surface areas for the oxides, As, maximal numbers of the molecules in the adsorbed clusters, thicknesses of the adsorbed liquid film and the free surface energies of the oxides in the absence of adsorption, γS0, were calculated using the ZAI equations. The As correlates well with SBET and it measures 77.5% of the SBET. The γS0 increases as the N2 average adsorption energy grows. The dependence between γS0 and CX (taking into account γS0 for X) is not obeyed for the mixed oxides. The γS0 for SiO2, Al2O3 and TiO2 rises as the permittivity and the index of refraction increase. The γS0 is within the range of dispersive components of free surface energy, which is determined by other experimental methods and calculated using the Lifshitz’ theory. The obtained parameters allow estimate the activity of the oxide surface with respect to trace gases in the Antarctic atmosphere that is necessary for calculating their partition coefficients between particles and the atmosphere and the kinetics of their removal. 


  1. Al-Abadleh, H. A., Grassian, V. H. 2003. Oxide surfaces as environmental interfaces. Surface Science Reports, 52. 63-161.
  2. Artaxo, P., Rabello, M. L. C. 1992. Trace elements and individual particle analysis of atmospheric aerosols from the Antarctic Peninsula. Tellus B., 44. 318-334.
  3. Asmi, E., Neitola, K., Teinilä, K., Rodriguez, E., Virkkula, A., Backman, J., et al. 2018. Primary sources control the variability of aerosol optical properties in the Antarctic Peninsula. Tellus B., 70:1414571.
  4. Atkins, C. B., Dunbar, G. B. 2009. Aeolian sediment flux from sea ice into southern McMurdo sound, Antarctica. Global Planetary Change, 69. 133-141.
  5. Ayling, B. F., McGowan, H. A. 2006. Niveo-eolian sediment deposits in coastal South Victoria Land, Antarctica: indicators of regional variability in weather and climate. Arctic, Antarctic and Alpine Research, 38. 313-324.[313:NSDICS]2.0.CO;2
  6. Basile, I., Grousset, F. E., Revel, M., Petit, J. R., Biscaye, P. E., Barkov, N. I. 1997. Patagonian origin of glacial dust deposited in East Antarctica (Vostok and Dome C) during glacial stages 2, 4 and 6. Earth Planet Science Letters, 146. 573-589.
  7. Bergstrom, L. 1997. Hamaker Constants of Inorganic Materials. Advances in Colloid and Interface Science, 70. 125-169.
  8. Bilinski, B.. Holysz, L. 1999. Some Theoretical and Experimental Limitations in the Determination of Surface Free Energy of Siliceous Solids. Powder Technology, 102. 120-126.
  9. Bogillo, V. I., Shkilev, V. P., Voelkel A. 1996. Chemical Heterogeneity of Metal Oxides Surface as Studied by Inverse Gas Chromatography at Finite Concentrations. Adsorption Science and Technology, 14(3). 189-198.
  10. Bogillo, V. I., Shkilev, V. P., Voelkel, A. 1998. Determination of Surface Free Energy Components for Heterogeneous Solids by Means of Inverse Gas Chromatography at Finite Concentrations. Journal of Materials Chemistry, 8(9). 1953-1961.
  11. Bogillo, V. I., Shkilev, V. P. 1999. Evaluation of Desorption Energy Distributions from TPD Spectra on the Heterogeneous Solid Surfaces. Journal of Thermal Analysis and Calorimetry, 55(2). 483-492.
  12. Bogillo, V. I., Bazylevska, M. S. 2008. Partitioning and Exc hange of Organochlorine Contaminants between Abiotic Compartments in Antarctica. In Mehmetli E. et al (eds). The Fate of Persistent Organic Pollutants in the Environment, Dordrecht: Springer. 333-351.
  13. Bory, A., Wolff, E., Mulvaney, R., Jagoutz, E., Wegner, A., Ruth, U., et al. 2010. Multiple sources supply eolian mineral dust to the Atlantic sector of coastal Antarctica: evidence from recent snow layers at the top of Berkner Island ice sheet. Earth Planet Science. Letters, 291. 138-148.
  14. Brunauer, S. Emmett, P. H., Teller, E. 1938. Adsorption of Gases in Multimolecular Layers. Journal of American Chemical Society, 60. 309-319.
  15. Budhavant, K., Safi, P. D., Rao, P. S. P. 2015. Sources and elemental composition of summer aerosols in the Larsemann Hills (Antarctica). Environmental Science and Pollution Research, 22. 2041-2050.
  16. Bullard, J. E., Baddock, M., Bradwell, T., Crusius, J., Darlington, E., Gaiero, D., et al. 2016. High-latitude dust in the Earth system. Review of Geophysics, 54. 447-485.
  17. Chaubey, J. P., Moorthy, K. K., Babu, S. S., Nair, V. S. 2011. The optical and physical properties of atmospheric aerosols over the Indian Antarctic stations during southern hemispheric summer of the international Polar Year 2007-2008. Annals of Geophysics, 29. 109-121.
  18. Chewings, J. M., Atkins, C., Dunbar, G., Golledge, N. R. 2014. Aeolian sediment transport and deposition in a modern high-latitude glacial marine environment. Sedimentology, 61. 1535-1557.
  19. Delmonte, B., Paleari, C. I., Andò, S., Garzanti, E., Andersson, P. S., Petit, J. R., et al. 2017. Causes of dust size variability in central East Antarctica (Dome B): atmospheric transport from expanded South American sources during marine isotope stage 2. Quaternary Science Review, 168. 55-68.
  20. Dupart, Y., King, S. M., Nekat, B., Nowak, A., Wiedensohler, A., Herrmann, H., David, G., Thomas, B., Miffre, A., Rairoux, P., D'Anna, B., George, C. 2012. Mineral Dust Photochemistry Induces Nucleation Events in the Presence of SO2. Proceedings of National Academy of Sciences of USA, 109(51). 20842-20847.
  21. Dzyaloshinskii, I.E., Lifshitz, E.M., Pitaevskii, L.P. 1961. The General Theory of Van der Waals Forces. Advances in Physics, 10. 165-209.
  22. Ghasemi, H., Ward, C. A. 2009. Determination of the Surface Tension of Solids in the Absence of Adsorption. Journal of Physical Chemistry, 113. 12632-12634.
  23. Gregg, S. J., Sing, K. S. V. 1982. Adsorption. Surface Area and Porosity, London. New York: Academic Press Inc.
  24. Gun'ko, V. M., Blitz, J. P., Gude, K., Zarko, V. I., Goncharuk, E. V., Nychiporuk, Y. M. Leboda, R., Skubiszewska-Zieba, J., Osovskii, V. D., Ptushinskii, Y. G., Mishchuk, O. A., Pakhovchishin, S. V., Gorbik, P. P. 2007. Surface Structure and Properties of Mixed Fumed Oxides. Journal of Colloid and Interface Science, 314(1). 119-130.
  25. Israelachvili, J.N. 1992. Adhesion Forces between Surfaces in Liquids and Condensable Vapours. Surface Science Reports, (14). 109-159.
  26. Kavan, J., Ondruch, J., Nývlt, D., Hrbá¡cek, F., Carrivick, J. L., Láska, K. 2017. Seasonal hydrological and suspended sediment transport dynamics in proglacial streams, James Ross Island, Antarctica. Geography Annals, 99. 38-55.
  27. Lancaster, N. 2002. Flux of eolian sediment in the McMurdo Dry Valleys, Antarctica: a preliminary assessment. Arctic, Antarctic and Alpine Research, 34. 318-323.
  28. Mauer, S., Mersmann, A., Peukert, W. 2001. Henry Coefficients of Adsorption Predicted from Solid Hamaker Constants. Chemical Engineering Science, 56. 3443-3453.
  29. Mazzera, D. M., Lowenthal, D., Chow, J. C., Watson, J. G., Grubisic, V. 2001. PM10 measurements at McMurdo station, Antarctica. Atmospheric Environment, 35. 1891-1902.
  30. McConnell, J. R., Aristarain, A. J., Banta, J. R., Edwards, P. R., Simoes, J. C. 2007. 20th-Century doubling in dust archived in an Antarctic peninsula ice core parallels climate change and desertification in South America. Proceedings of National Academy of Sciences of U. S. A., 104. 5743-5748.
  31. Medout-Marere, V. 2000. A Simple Experimental Way of Measuring the Hamaker Constant A11 of Divided Solids by Immersion Calorimetry in Apolar Liquids. Journal of Colloid and Interface Science, 228. 434-437.
  32. Ne, P. D., Bertler, N. A. N. 2015. Trajectory modeling of modern dust transport to the Southern Ocean and Antarctica. Journal of Geophysics Research Atmosphere, 120. 9303-9322.
  33. Pereira, K. C. D., Evangelista, H., Pereira, E. B., Simoes, J. C., Johnson, E., Melo, L. R. 2004. Transport of crustal microparticles from chilean Patagonia to the Antarctic peninsula by SEM-EDS analysis. Tellus B., 56. 262-275.
  34. Pokrovskiy, V. A., Bogillo, V. I., Dabrowski, A. 1999. Adsorption and Chemisorption of Organic Pollutants on the Solid Aerosols Surface. In. Dabrowski A. (ed). Adsorption and its Application in Industry and Environmental Protection. Amsterdam: Elsevier. 571-634.
  35. Prausnitz, J. M. 1966. Surface Tension of Simple Liquids. Transactions of Faraday Society, 62. 1097-1104.
  36. Pyziy, A. M., Volcov, V. B., Poznayeva, O. A., Bogillo, V. I. Shkilev, V. P. 1997. Comparison of Various Numerical Procedures for Analysis of Structural Heterogeneity. Langmuir, 13(5). 1303-1306.
  37. Seinfeld, J.H., Pandis, S. N. 2006. Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, London, New York: John Wiley & Sons, Inc.
  38. Truzzi, C., Lambertucci, L., Illuminati, S., Annibaldi, A., Scarponi, G. 2005. Direct gravimetric measurements of the mass of the Antarctic aerosol collected by high volume sampler: PM10 summer seasonal variation at Terra Nova Bay. Annals of Chemistry, 95. 867-876.
  39. Weller, R., Wöltjen, J., Piel C., Resenberg, R., Wagenbach, D., König-Langlo, G., et al. 2008. Seasonal variability of crustal and marine trace elements in the aerosol at Neumayer station, Antarctica. Tellus B., 60. 742-752.
  40. Zandavi, S. H. Ward, C. A. 2014. Clusters in the Adsorbat es of Vapours and Gases: Zeta Isotherm Approach. Physical Chemistry and Chemical Physics, 16. 10979-10989.