Abstract
The Al13 polycation is the predominant hydroxy-Al species in partially neutralized solutions. However, the existence of the Al13 species and the factors governing its formation in terrestrial environments still remain obscure. The objective of this study was to investigate the influence of pyrogallol, a common polyphenol in soils, on the formation of Al13 tridecamer. Hydroxy-Al solutions with an OH/Al molar ratio of 2.2 (pH 4.53) at pyrogallol/Al molar ratios of 0, 0.01, 0.05, 0.1 and 0.5 were prepared and mixed with 0.5 M sodium sulfate to form aluminum sulfate precipitation products. The solid-state 27Al nuclear magnetic resonance (NMR) spectra of the precipitates show that the pyrogallol perturbed the formation of Al13 tridecamer species as indicated by the decrease in the intensity of resonance peak, observed at 62.5 ppm, with increase in the pyrogallol/Al molar ratio. The crystallization of the precipitated Al sulfates was also hampered by pyrogallol, resulting in the formation of X-ray non-crystalline products at a pyrogallol/Al molar ratio of 0.50. The absorbance at 465 and 650 nm of the hydroxy-Al-pyrogallol solutions, the C coprecipitated, the electron spin resonance and 13C CPMAS-NMR spectra of the precipitates indicate the concomitant enhanced abiotic humification of pyrogallol by the X-ray amorphous Al species.
Similar content being viewed by others
References
Akitt, J.W. (1989) Multinuclear studies of aluminum compounds. Progress in NMR Spectroscopy, 21, 1–139.
Akitt, J.W. and Elders, J.M. (1988) Multinuclear magnetic resonance studies of the hydrolysis of aluminum (III). VIII. Base hydrolysis monitored at very high magnetic field. Journal of Chemical Society, Dalton Transactions, 1347–1356.
Akitt, J.W. and Farthing, A.J. (1981) Aluminum-27 nuclear magnetic resonance studies of the hydrolysis of aluminum (III). IV. Hydrolysis using sodium carbonate. Journal of Chemical Society, Dalton Transactions, 1617–1625.
Akitt, J.W., Greenwood, N.N., Khandelwal, B.L. and Lester, G.D. (1972) 27Al nuclear magnetic resonance studies of the hydrolysis and polymerization of the hexa-aqua-aluminum (III) cation. Journal of Chemical Society, Dalton Transactions, 604–610.
Azaroff, L.V. and Buerger, M.J. (1958) The Powder Method in X-ray Crystallography. McGraw Hill Inc., New York, 342 pp.
Bassett, H. and Goodwin, T.H. (1949) The basic aluminum sulfates. Journal of Chemical Society (London), 2239–2279.
Bersillon, J.L., Hsu, P.H. and Fiessinger, F. (1980) Characterization of hydroxy-aluminum solutions. Soil Science Society of America Journal, 44, 630–634.
Bertsch, P.M. (1987) Conditions for Al13 polymer formation in partially neutralized aluminum solutions. Soil Science Society of America Journal, 51, 825–828.
Bertsch, P.M. (1989) Aluminum speciation: methodology and applications. Pp. 63–105 in: Advances in Environmental Sciences. Acidic Precipitation, Vol. 4: Soils, Aquatic Processes, and Lake Acidification (D.C. Adriano and W. Salomons, editors). Springer-Verlag, New York.
Bertsch, P.M. and Parker, D.R. (1996) Aqueous polynuclear aluminum species. Pp. 117–168 in: The Environmental Chemistry of Aluminum (G. Sposito, editor). CRC Press, Lewis Publishers, Boca Raton, Florida.
Bertsch, P.M., Layton, W.J. and Barnhisel, R.I. (1986a) Speciation of hydroxyaluminum solutions by wet chemical and aluminum-27 NMR methods. Soil Science Society of America Journal, 50, 1449–1454.
Bertsch, P.M., Thomas, G.W. and Barnhisel, R.L. (1986b) Characterization of hydroxyaluminum solutions by aluminum-27 nuclear magnetic resonance spectroscopy. Soil Science Society of America Journal, 50, 825–828.
Bottero, J.Y., Cases, J.M., Fiessinger, F. and Peinier, J.E. (1980) Studies of hydrolyzed aluminum chloride solutions. I. Nature of aluminum species and composition of aqueous solutions. Journal of Physical Chemistry, 84, 2933–2939.
Bottero, J.Y., Axelos, M., Tchoubar, D., Cases, J.M., Fripiat, J.J. and Fiessinger, F. (1987) Mechanism of formation of aluminum trihydroxide from Keggin Al13 polymers. Journal of Colloid and Interface Science, 117, 47–57.
Flatten, T.P. and Garruto, R.M. (1992) Polynuclear ions in aluminum toxicity. Journal of Theoretical Biology, 156, 129–132.
Furrer, G., Phillips, B.L., Ulrich, K.-U., Pothie, R. and Casey, W.H. (2002) The origin of aluminum floes in polluted streams. Science, 297, 2245–2247.
Hatcher, P.G., Schnitzer, M., Dennis, L.W. and Maciel, G.E. (1981) Aromaticity of humic substances in soils. Soil Science Society of America Journal, 45, 1089–1094.
Hayes, M.H.B. and Swift, R.S. (1978) The chemistry of soil organic colloids. Pp. 179–320 in: The Chemistry of Soil Constituents (D.J. Greenland and M.H.B. Hayes, editors). John Wiley and Sons, New York.
Hiradate, S., Taniguchi, S. and Sakurai, K. (1998) Aluminum speciation in aluminum-silica solutions and potassium chloride extracts of acidic soils. Soil Science Society of America Journal, 62, 630–636.
Holland, T.J.B. and Redfern, S.A.T. (1997) Unit cell refinement from powder diffraction data: The use of regression diagnostics. Mineralogical Magazine, 61, 65–67.
Huang, P.M. (1988) Ionic factors affecting aluminum transformations and the impact on soil and environmental sciences. Advances in Soil Science, 8, 1–78.
Huang, P.M. (1990) The role of soil minerals in influencing transformations of natural organics and xenobiotics in the environment. Pp. 29–115 in: Soil Biochemistry, Vol. 6 (J.-M. Bollag and G. Stotzky, editors). Marcel Dekker, New York.
Huang, P.M. and Bollag, J.-M. (1999) Minerals-organics-microorganisms interactions in the soil environment. Pp. 3–39 in: Structure and Surface Reactions of Soil Particles (P.M. Huang, N. Senesi and J. Buffle, editors). IUPAC Series on Analytical and Physical Chemistry of Environmental Systems, John Wiley & Sons, Chichester, UK.
Huang, P.M., Wang, M.K., Kampf, N. and Schulze, D.G. (2002) Aluminum hydroxides. Pp. 261–289 in: Soil Mineralogy with Environmental Applications (J.B. Dixon and D.G. Schulze, editors). Soil Science Society of America, Madison, Wisconsin.
Hunter, D. and Ross, D.S. (1991) Evidence for a phytotoxic hydroxy-aluminum polymer in organic soil horizons. Science, 251, 1056–1058.
Johansson, G. (1960) On the crystal structures of some basic aluminum sulfates. Acta Chemica Scandinavica, 14, 771–773.
Johansson, G., Lundgren, G., Sillen, L.G. and Soderquist, R. (1960) On the crystal structure of a basic aluminum sulfate and the corresponding selenate. Acta Chemica Scandinavica, 14, 769–771.
Kerven, G.L., Larsen, P.L. and Blarney, F.P.C. (1995) Detrimental sulfate effects on formation of Al13 tridecameric polycation in synthetic soil solutions. Soil Science Society of America Journal, 59, 765–771.
Krishnamurti, G.S.R., Wang, M.K. and Huang, P.M. (1999) Role of tartaric acid in the inhibition of the formation of Al13 tridecamer using sulfate precipitation. Clays and Clay Minerals, 47, 658–663.
Kunwar, A.C., Thompson, A.R., Gutowsky, H.S. and Oldfield, E. (1984) Solid state aluminum-27 NMR studies of tridecameric Al-oxo-hydroxy clusters in basic aluminum selenate, sulfate, and the mineral zunyite. Journal of Magnetic Resonance, 60, 467–474.
Larsen, P.L., Kerven, G.L. and Edwards, D.G. (1995) Effects of silicic acid in the chemistry of monomeric and polymeric (Al13) aluminum species in solution. Pp. 617–621 in: Plant Soil Interactions at Low pH (R.A. Date et al., editors). Kluwer Academic Publishers, Dordrecht, The Netherlands.
Lothenbach, B., Furrer, G. and Schulin, R. (1997) Immobilization of heavy metals by polynuclear aluminum and montmorillonite compounds. Environmental Science and Technology, 31, 1452–1462.
Masion, A., Bottero, J.Y., Thomas, F. and Tchoubar, D. (1994a) Chemistry and structure of Al(OH)/organic precipitates. A small-angle X-ray scattering study. 2. Speciation and structure of aggregates. Langmuir, 10, 4349–4352.
Masion, A., Tchoubar, D., Bottero, J.Y., Thomas, F. and Villiéras, F. (1994b) Chemistry and structure of Al(OH)/organic precipitates. A small angle X-ray scattering study. 1. Numerical procedure for speciation from scattering curves. Langmuir, 10, 4344–4348.
Masion, A., Thomas, F., Tchoubar, D., Bottero, J.Y. and Tekely, P. (1994c) Chemistry and structure of Al(OH)/organic precipitates. A small-angle X-ray scattering study. 3. Depolymerization of the Al13 polycation by organic ligands. Langmuir, 10, 4353–4356.
McKeague, J.A., Cheshire, M.V., Andreaux, F. and Berthelin, J. (1986) Organo-mineral complexes in relation to pedogenesis. Pp. 549–592 in: Interactions of Soil Minerals with Natural Organics and Microbes (P.M. Huang and M. Schnitzer, editors). SSSA Special Publication 17, Soil Science Society of America, Madison, Wisconsin.
Mueller, D., Gessner, W., Schonherr, S. and Gorz, H. (1981) Basic aluminum salts and their solutions. X. NMR-investigations on the tridecameric aluminum-oxohydroxy cation. Zeitschrift für Annorganische und Allgemeine Chemie, 483, 153–160.
Parker, D.R. and Bertsch, P.M. (1992a) Identification and quantification of the “Al13” tridecameric polycation using Ferron. Environmental Science and Technology, 26, 908–914.
Parker, D.R. and Bertsch, P.M. (1992b) Formation of the “Al13” tridecameric polycation under diverse synthesis conditions. Environmental Science and Technology, 26, 914–921.
Parker, D.R., Kinraide, T.B. and Zelazny, L.W. (1989) On the phytotoxicity of polynuclear hydroxy-aluminum complexes. Soil Science Society of America Journal, 53, 789–796.
Poleo, A.B.S. (1995) Aluminum polymerization — a mechanism of acute toxicity of aqueous aluminum to fish. Aquatic Toxicology, 31, 347–352.
Ross, D.S., Bartlett, R.J. and Zhang, H. (2001) Photochemically induced formation of the ‘Al13’ tridecameric polycation in the presence of Fe(III) and organic acids. Chemosphere, 44, 827–832.
Schnitzer, M. (1978) Recent findings on the characterization of humic substances extracted from soils from widely different climatic zones. IAEA-SM-211/7, Soil Organic Matter Studies. Vol. II, IAEA, Vienna, pp. 117–130.
Schnitzer, M., Barr, M. and Hortenstein, R. (1984) Kinetics and characteristics of humic acids produced from simple phenols. Soil Biology and Biochemistry, 16, 371–376.
Shann, J.R. and Bertsch, P.M. (1993) Differential cultivar response to polynuclear hydroxy-aluminum complexes. Soil Science Society of America Journal, 57, 116–120.
Shindo, H. and Huang, P.M. (1982) Role of Mn(IV) oxide in abiotic formation of humic substances in the environment. Nature, 298, 363–365.
Shindo, H. and Huang, P.M. (1984) Catalytic effects of manganese (IV), iron (III), aluminum and silicon oxides on the formation of phenolic polymers. Soil Science Society of America Journal, 48, 927–934.
Stevenson, F.J. (1994) Humus Chemistry, 2nd edition. John Wiley & Sons, New York.
Thomas, F., Masion, A., Bottero, J.Y., Rouiller, J., Genevrier, F. and Boudot, D. (1991) Aluminum(III) speciation with acetate and oxalate. A Potentiometric and 27Al NMR study. Environmental Science and Technology, 25, 1553–1559.
Thomas, F., Masion, A., Bottero, J.Y., Rouiller, J., Montigny, F., and Genevrier, F. (1993) Aluminum(III) speciation with hydroxy carboxylic acids. 27Al NMR study. Environmental Science and Technology, 27, 2511–2516.
Thompson, A.R., Kunwar, A.C., Gutowsky, H.S. and Oldfield, E. (1987) Oxygen-17 and aluminum-27 nuclear magnetic resonance spectroscopic investigations of aluminum (III) hydrolysis products. Journal of Chemical Society, Dalton Transactions, 2317–2322.
Tsai, P.P. and Hsu, P.H. (1984) Studies of aged OH-Al solutions using kinetics of Al-ferron reactions and sulfate precipitation. Soil Science Society of America Journal, 48, 59–65.
Vance, G.F., Stevenson, F.J. and Sikora, F.J. (1996) Environmental chemistry of aluminum-organic complexes. Pp. 169–220 in: The Environmental Chemistry of Aluminum (G. Sposito, editor). CRC Press, Lewis Publishers, Boca Raton, Florida.
Violante, A., Krishnamurti, G.S.R. and Huang, P.M. (2002) Impact of organic substances on the formation and transformation of metal oxides in soil environments. Pp. 133–188 in: Interactions between Soil Particles and Microorganisms. Impact on the Terrestrial Ecosystem (P.M. Huang, J.-M. Bollag and N. Senesi, editors). IUPAC Series on Analytical and Physical Chemistry of Environmental Systems, Vol. 8. John Wiley & Sons, Chichester, UK.
Wang, D. and Anderson, D.W. (1998) Direct measurement of organic carbon content in soils by the Leco 12 carbon analyzer. Communications in Soil Science and Plant Analysis, 29, 15–21.
Wang, M.C. and Huang, P.M. (2000) Characteristics of pyrogallol-derived polymers formed by catalysis of oxides. Soil Science, 165, 737–747.
Wang, T.S.C., Huang, P.M., Chou, C.-H. and Chen, J.-H. (1986) The role of soil minerals in the abiotic polymerization of phenolic compounds and formation of humic substances. Pp. 251–285 in: Interactions of Soil Minerals with Natural Organics and Microbes (P.M. Huang and M. Schnitzer, editors). SSSA Special Publication 17, Soil Science Society of America, Madison, Wisconsin.
Wertz, J.E. and Bolton, J.R. (1972) Electron Spin Resonance — Elementary Theory and Practical Applications. McGraw Hill Inc., New York, 497 pp.
Wilson, MA. and Goh, K.M. (1977) Proton-decoupled pulse Fourier-transform 13C NMR spectra of soil organic matter. Journal of Soil Science, 28, 645–652.
Yamaguchi, N.U., Hiradate, S., Mizoguchi, M. and Miyazaki, T. (2003) Formation and disappearance of Al tridecamer in the presence of low molecular weight organic ligands. Soil Science and Plant Nutrition, 49, 551–556.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Krishnamurti, G.S.R., Wang, M.K. & Huang, P.M. Effects of Pyrogallol on Al13 Tridecamer Formation And Humification. Clays Clay Miner. 52, 734–741 (2004). https://doi.org/10.1346/CCMN.2004.0520608
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1346/CCMN.2004.0520608