Abstract
Chemical thermodynamics augmented by the Gay-Lussac-Ostwald step rule provides a theoretical approach to weathering phenomena in soils that requires few ad hoc constitutive assumptions. The efficacy of this approach is illustrated with several examples of natural and anthropogenically-induced weathering reactions involving kaolinite. In soils, kaolinite exhibits a continuum of structural disorder that is reflected by a corresponding spectrum of solubility product constants. The composition of the soil solution vis-à-vis this spectrum can be interpreted with the help of the step rule. The concept of a soil kaolinite continuum appears necessary to the evaluation of activity-ratio diagrams and other thermodynamic constructs.
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References
Sposito, G. 1981, “The Thermodynamics of Soil Solutions”, Clarendon Press, Oxford.
Sposito, G. 1984, “Thermodynamics of the soil solution”, in “Soil Physical Chemistry”, D. L. Sparks, ed., C. R. C. Press, Boca Raton.
Lindsay, W. L. 1979, “Chemical Equilibria in Soils”, John Wiley, New York.
Stumm, W. and Morgan, J. J. 1981, “Aquatic Chemistry”, John Wiley, New York.
Lewis, G. N. and Randall, M. 1923, “Thermodynamics and the Free Energy of Chemical Substances”, McGraw-Hill, New York.
Hemingway, B. S. 1982, “Gibbs free energies of formation of Bayerite, Nordstrandite, A1(0H)2+, and A1(0H)2, aluminum mobility, and the formation of bauxites and laterites,” Advan. Phys. Geochem. 2, pp. 285–316.
Dixon, J. B. and Weed, S. B. 1977, “Minerals in Soil Environments”, Soil Science Society of America, Madison.
Kittrick, J. A. 1980, “Gibbsite and kaolinite solubilities by immiscible displacement of equilibrium solutions,” Soil Sci. Soc. Am. J. 44, pp. 139–142.
Karathansas, A. D. and Hajek, B. F. 1983, “Transformation of smectite to kaolinite in naturally acid soil systems: Structural and thermodynamic considerations,” Soil Sci. Soc. Am. J. 47, pp. 158–163.
Karathanasis, A. D., Adams, F. and Hajek, B. F. 1983, “Stability relationships in kaolinite, gibbsite, and Al- hydroxy interlayered vermiculite soil,” Soil Sci. Soc. Am. J. 47, pp. 1247–1251.
Bourrie, G. and Grimaldi, C. 1979, “Premiers resultats concernant la composition chimique des solutions issues de sols bruns acides sur granite en climat tempere oceanique: Donnees naturelles et experimentales,” in “Migrations Organo-Minerales dans les Sols Temp£res”, Colloques international du C.N.R.S., no. 303, pp. 41–8.
Singer, A. and Navrot, J. 1977, “Clay formation from basic volcanic rocks in a humid Mediterranean climate,” Soil Sci. Soc. Am. J. 41, pp. 645–650.
Aurousseau, P., Curmi, P. and Charpentier, S. 1983, “Les vermiculites hydroxy-alumineuses dans des sols et les formations d’alteration du massif Armoricain: Approches mineralogique, microanalytique et thermodynamique,” Geoderma 31, pp. 17–40.
Brindley, G. W. 1980, “Order-disorder in clay mineral structures,” in “Crystal Structures of Clay Minerals and their X-ray Identification”, G. W. Brindley and G. Brown, Mineralogical Society, London, pp. 125–195.
Wagman, D. D., Evans, W. H., Parker, V. B., Schumm, R. H., Halow, I., Bailey, S. M., Churney, K. L. and Nuttall, R. L. 1982, “The NBS tables of chemical thermodynamic properties,” J. Phys. Chem. Ref. Data 11, Supp. 2, pp. 1–392.
Calvert, C. S., Buol, S. W. and Weed, S. B. 1980, “Mineralogical characteristics and transformations of a vertical rock-saprolite-soil sequence in the North Carolina Piedmont: II. Feldspar alteration products-their transformations through the profile,” Soil Sci. Soc. Am. J. 44, pp. 1104–1112.
Weaver, C. E. and Pollard, L. D. 1973, “The Chemistry of Clay Minerals”, Elsevier, Amsterdam.
Misra, U. K. and Upchurch, W. J. 1976, “Free energy of formation of beidellite from apparent solubility measurements,” Clays and Clay Min. 24, pp. 327–331.
Bassett, R. L., Kharaka, Y. K. and Langmuir, D. 1979, “Critical review of the equilibrium constants for kaolinite and sepiolite,” in “Chemical Modeling in Aqueous Systems”, E. A. Jenne, ed., Am. Chem. Soc., Washington, D.C., pp. 389–400.
Marshall, C. E., Chowdhury, M. Y. and Upchurch, W. J. 1973, “Lysimetric and chemical investigations of pedological changes. Part 2. Equilibration of profile samples with aqueous solutions,” Soil Sci. 116, pp. 336–358.
Misra, U. K., Upchurch, W. J. and Marshall, C. E. 1976, “Lysimetric and chemical investigations of pedological changes: Part 3. Relative changes in the potassium- and magnesium-treated profiles and leaching losses,” Soil Sci. 121, pp. 323–331.
Misra, U. K., Upchurch, W. J. and Marshall, C. E. 1976, “Lysimetric and chemical investigations of pedological changes: Part 4. Mineral equilibria in relation to potassium- and magnesium-enriched environment in the profile,” Soil Sci. 122, pp. 25–35.
Mattigod, S. V. and Sposito, G. 1978, “Improved method for estimating the standard free energies for formation (AGf,298.15) of smectites,” Geochim. et Cosmochim. Acta 42, pp. 1753–1762.
Kirkland, D. L. and Hajek, B. F. 1972, “Formula derivation of Al-interlayered vermiculite in selected soil clays,” Soil Sci. 114, pp. 317–322.
Veith, J. A. and Sposito, G. 1977, “Reactions of alumino- silicates, aluminum hydrous oxides, and aluminum oxide with o-phosphate: The formation of X-ray amorphous analogs of variscite and montebrasite,” Soil Sci. Soc. Am. J. 41, pp. 870–876.
Pavan, M. A., Bingham, F. T. and Pratt, P. R. 1984, “Redistribution of exchangeable calcium, magnesium, an aluminum following lime or gypsum applications to a Brazilian Oxisol,” Soil Sci. Soc. Am. J. 48, pp. 33–38.
Nordstrom, D. K. 1982, “The effect of sulfate on aluminum concentrations in natural waters: Some stability relations in the sytem A12O3-SO3-H2O at 298 K,” Geochim. et Cosmochim. Acta 46, pp. 681 - 692.
Kittrick, J. A. 1973, “Mica-derived vermiculites as unstable intermediates,” Clays and Clay Min. 21, pp. 479–488.
Henderson, J. A., Doner, H. E., Weaver, R. M., Syers, J. K. and Jackson, M. L. 1976, “Cation and silica relationships of mica weathering to vermiculite in calcareous Harps soil,” Clays and Clay Min. 24, pp. 93–100.
Lippmann, F. 1977, “The solubility products of complex minerals, mixed crystals, and three-layer clay minerals,” N. Jb. Miner. Abh. 130, pp. 243–263.
Lippmann, F. 1982, Proc. Int. Clay Conf. 1981, “The thermodynamic status of clay minerals,” pp. 475–485.
Aagard, P. and Helgeson, H. C. 1983, “Activity/composition relations among silicates and aqueous solutions: II. Chemical and thermodynamic consequences of ideal mixing of atoms on homological sites in montmorillonites, illites, and mixed-layer clays,” Clays and Clay Min. 31, pp. 207–217.
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Sposito, G. (1985). Chemical Models of Weathering in Soils. In: Drever, J.I. (eds) The Chemistry of Weathering. Nato ASI Series, vol 149. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-5333-8_1
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DOI: https://doi.org/10.1007/978-94-009-5333-8_1
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