Abstract
Adsorption complexes of humic substances with soil minerals comprise the bulk of organic matter in humus horizons of cold and temperate soils. They represent the most stable Corg fraction in soils with mean residence time of 102–103 years. A considerable fraction of adsorbed organic matter is represented by high molecular weight (50–100 kDa) humic acid–like polymers. The concept of sorptive preservation cannot explain the origin of such polymers on mineral surfaces, because their migration to adsorption sites should be limited by low solubility. It can be suggested that high molecular weight humic acid–like polymers are formed in situ in mineral soil horizons. A possible mechanism is heterophase polymerization of low molecular weight (and thus soluble) precursor material in presence of catalytically active solid phases. The chapter summarizes available data supporting the concept of surface polymerization of humic acids and provides an evidence for the key role of immobilized phenol oxidases and solid matrix in accelerating this process.
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Ahn MY, Martinez CE, Archibald DD, Zimmerman AR, Bollag JM, Dec J (2006) Transformation of catechol in presence of a laccase and birnessite. Soil Biol Biochem 38:1015–1020
Ahn MY, Zimmerman AR, Martinez CE, Archibald DD, Bollag JM, Dec J (2007) Characteristics of Trametes villosa laccase adsorbed on aluminum hydroxide. Enzym Microb Technol 41:141–148
Allison SD, Jastrow JD (2006) Activities of extracellular enzymes in physically isolated fractions of restored grassland soils. Soil Biol Biochem 38:3245–3256
Arnarson TS, Keil RG (2001) Organic-mineral interactions in marine sediments studied using density fractionation and X-ray photoelectron spectroscopy. Org Geochem 32:1401–1415
Batjes NH (1996) Total carbon and nitrogen in the soils of the world. Eur J Soil Sci 47:151–163
Bollag JM, Minard RD, Liu SY (1983) Cross-linkage between anilines and phenolic humus constituents. Environ Sci Technol 17:72–80
Bollag JM, Meyers C, Pal S, Huang PM (1995) The role of abiotic and biotic catalysts in the transformation of phenolic compounds. In: Huang PM, Berthelin J, Bollag JM, McGill WB, Page AL (eds) Environmental impact of soil component interactions, vol 1. CRS/Lewis, Boca Raton, FL, pp 299–310
Bollag JM, Dec J, Huang PM (1998) Formation mechanisms of complex organic structures in soil habitats. Adv Agron 63:237–265
Boufi S, Gandini A (2002) Formation of polymeric films on cellulosic surfaces by admicellar polymerization. Cellulose 8:303–312
Cecchi AM, Koskinen WC, Cheng HH, Haider K (2004) Sorption-desorption of phenolic acids as affected by soil properties. Biol Fertil Soils 39:235–242
Christensen BT (2001) Physical fractionation of soil and structural and functional complexity in organic matter turnover. Eur Soil Sci 52:345–353
Colarieti ML, Toscano G, Ardi MR, Greco G (2006) Abiotic oxidation of catechol by soil metal oxides. J Hazard Mater 134:161–168
Criquet S, Farnet AM, Tagger S, Le Petit J (2000) Annual variations of phenoloxidase activities in an evergreen oak litter: influence of certain biotic and abiotic factors. Soil Biol Biochem 32:1505–1513
Dalton BR, Blum U, Weed SB (1989) Plant phenolic acids in soils: sorption of ferulic acid by soil and soil components sterilized by different techniques. Soil Biol Biochem 21:1011–1018
Danielewicz-Ferchmin I, Ferchmin AR (2004) Water at ions, biomolecules and charged surfaces. Phys Chem Liq 42:1–36
Di Nardo C, Cinquegrana A, Papa S, Fuggi A, Fioretto A (2004) Laccase and peroxidase isoenzymes during leaf litter decomposition of Quercus ilex in a Mediterranean ecosystem. Soil Biol Biochem 36:1539–1544
Fedorova S, Stejskal J (2002) Surface and precipitation polymerization of aniline. Langmuir 18:5630–5632
Fenner N, Freeman C, Reynolds B (2005) Hydrological effects on the diversity of phenolic degrading bacteria in a peatland: implications for carbon cycling. Soil Biol Biochem 37:1277–1287
Flaig W (1966) The chemistry of humic substances. In: The use of isotopes in soil organic matter studies, Report of FAO/IAEA Technical Meeting. Pergamon, New York, pp 103–127
Gallet C, Pellissier F (1997) Phenolic compounds in natural solutions of the coniferous forest. J Chem Ecol 23:2401–2411
Gerstner JA, Bell JA, Cramer SM (1994) Gibbs free energy of adsorption of biomolecules in ion-exchange systems. Biophys Chem 52:97–106
Gonzalez JM, Laird DA (2004) Role of smectites and Al-substituted goethites in the catalytic condensation of arginine and glucose. Clays Clay Miner 52:443–450
Gramss G, Voigt KD, Kirsche B (1998) Oxidoreductase enzymes liberated by plant roots and their effects on soil humic material. Chemosphere 38:1481–1494
Guggenberger G, Kaiser K (2003) Dissolved organic matter in soil: challenging the paradigm of sorptive preservation. Geoderma 113:293–310
Huang PM (2000) Abiotic catalysis. In: Summer ME (ed) Handbook of soil science. CRC Press LLC, Boca Raton, FL, pp 303–334
Huang Q, Weber WJ (2004) Peroxidase-catalyzed coupling of phenol in the presence of model inorganic and organic solid phases. Environ Sci Technol 38:5238–5245
Huang PM, Wang MK, Kampf N, Schulze DG (2002a) Aluminum hydroxides. In: Dixon JB, Schulze DG (eds) Soil mineralogy with environmental applications. Soil Science Society of America, Madison, WI, USA, pp 261–289
Huang Q, Selig H, Weber WJ (2002b) Peroxidase-catalyzed oxidative coupling of phenols in the presence of geosorbents: rates of non-extractable product formation. Environ Sci Technol 36:596–602
Kalbitz K, Solinger S, Park JH, Michalzik B, Matzner E (2000) Controls on the dynamics of dissolved organic matter in soils: a review. Soil Sci 165:277–304
Klavinš M (1997) Aquatic humic substances: characterization, structure and genesis. University of Latvia, Riga, 234 p
Kleber M, Sollins S, Sutton RA (2007) A conceptual model of organo-mineral interactions in soils: self-assembly of organic molecular fragments into multilayered structures on mineral surfaces. Biogeochem 85:9–24
Kononova MM (1966) Soil organic matter. Pergamon, Oxford
Kuvaeva YV (1980) The content and composition of phenolic acids in some soils of non-chernozemic zone. Sov Soil Sci 1:97–106
Lambert JF (2008) Adsorption and polymerization of amino acids on mineral surfaces: a review. Orig Life Evol Biosph 38:211–242
Lehmann RG, Cheng HH (1988) Reactivity of phenolic acids in soil and formation of oxidation products. Soil Sci Soc Am J 52:1304–1309
Lehmann RG, Cheng HH, Harsh JB (1986) Oxidation of phenolic acids by soil iron and manganese oxides. Soil Sci Soc Am J 51:352–356
Leontievsky AA, Myasoedova NM, Baskunov BP, Pozdnyakova NN, Vares T, Kalkkinen N et al (1999) Reactions of blue and yellow fungal laccases with lignin model compounds. Biochemistry (Moscow) 64:1150–1156
Liu C, Huang PM (2002) Role of hydroxy-aluminosilicate ions (proto-imogolite sol) in the formation of humic substances. Org Geochem 33:295–305
Liu SY, Freyer AJ, Minard RD, Bollag JM (1985) Enzyme-catalyzed complex formation of amino acid esters and phenolic humus constituents. Soil Sci Soc Am J 49:337–342
Matocha CJ, Sparks DL, Amonette JE, Kukkadapu RK (2001) Kinetics and mechanism of birnessite reduction by catechol. Soil Sci Soc Am J 65:58–66
McBride MB (1987) Adsorption and oxidation of phenolic compounds by iron and manganese oxides. Soil Sci Soc Am J 51:1466–1472
Mikutta R, Kleber M, Torn MS, Jahn R (2006) Stabilization of soil organic matter: association with minerals or chemical recalcitrance? Biogeochemistry 77:25–56
Naidja A, Huang PM (2002) Significance of the Henri-Michaelis-Menten theory in abiotic catalysis: catechol oxidation by δ-MnO2. Surface Sci 506:243–249
Naidja A, Huang PM, Bollag JM (1997) Activity of tyrosinase immobilized on hydroxyaluminum-montmorillonite complexes. J Mol Catal A 115:305–316
Naidja A, Huang PM, Bollag JM (1998) Comparison of reaction products from the transformation of catechol catalyzed by birnessite or tyrosinase. Soil Sci Soc Am J 62:188–195
Nannipieri P, Gianfreda L (1998) Kinetics of enzyme reactions in soil environments. In: Huang PM, Senesi N, Buffle J (eds) Environmental particles – structure and surface reactions of soil particles. Wiley, Chichester, pp 449–479
Pal S, Bollag JM, Huang PM (1994) Role of abiotic and biotic catalysts in the transformation of phenolic compounds through oxidative coupling reactions. Soil Biol Biochem 26:813–820
Perdue EM, Ritchie JD (2004) Dissolved organic matter in freshwaters. In: Holland HD, Turekian KK (eds) Treatise on geochemistry. Elsevier, Amsterdam, pp 273–318
Pohlman AA, McColl JG (1989) Organic oxidation and manganese and organic mobilization in forest soils. Soil Sci Soc Am J 53:686–690
Quiquampoix H, Servagent-Noinville S, Baron M (2002) Enzyme adsorption on soil mineral surfaces and consequences for the catalytic activity. In: Burns RG, Dick RP (eds) Enzymes in the environment. Marcel Dekker, New York, pp 285–306
Rittstieg K, Suurnakki A, Suortti T, Kruus K, Guebitz G, Buchert J (2002) Investigations on the laccase-catalyzed polymerization of lignin model compounds using size-exclusion HPLC. Enzyme Microb Technol 31:403–410
Sapurina I, Osadchev AY, Volchek BZ, Trchova M, Riede A, Stejskal J (2002) In-situ polymerized polyaniline films: 5. Brush-like chain ordering. Synth Met 129:29–37
Sapurina I, Fedorova S, Stejskal J (2003) Surface polymerization and precipitation polymerization of aniline in presence of sodium tungstate. Langmuir 19:7413–7416
Sarkar JM, Leonowicz A, Bollag JM (1989) Immobilization of enzymes on clays and soils. Soil Biol Biochem 21:223–230
Schulze DG (2002) An introduction to soil mineralogy. In: Dixon JB, Schulze DG (eds) Soil mineralogy with environmental applications. Soil Science Society of America, Madison, WI, pp 1–36
Shindo H (1990) Catalytic synthesis of humic acids from phenolic compounds by Mn(IV) oxide (birnessite). Soil Sci Plant Nutr 4:679–682
Shindo H, Huang PM (1984) Catalytic effects of manganese (IV), iron (III), aluminum and silicon oxides on the formation of phenolic polymers. Soil Sci Soc Am J 48:927–934
Shindo H, Huang PM (1985) Catalytic polymerization of hydroquinone by primary minerals. Soil Sci 139:505–511
Sjoblad RD, Bollag JM (1981) Oxidative coupling of aromatic compounds by enzymes from soil microorganisms. In: Paul EA, Ladd JN (eds) Soil biochemistry, vol 5. Marcel Dekker, New York, pp 113–152
Snajdr J, Valaskova V, Merhautova V, Herinkova J, Cajthaml T, Baldrian P (2008) Spatial variability of enzyme activities and microbial biomass in the upper layers of Quercus petraea forest soil. Soil Biol Biochem 40:2068–2075
Stevenson FJ (1994) Humus chemistry: genesis, composition, reactions, 2nd edn. Wiley, New York
Stone AT, Morgan JJ (1984) Reduction and dissolution of manganese (III) and manganese (IV) oxides by organics: 1. Reaction with hydroquinone. Environ Sci Technol 18:450–456
Tietjen T, Wetzel RG (2003) Extracellular enzyme-clay mineral complexes: enzyme adsorption, alteration of enzyme activity and protection from photodegradation. Aquat Ecol 37:331–339
Tipping E, Cooke D (1982) The effects of adsorbed humic substances on the surface charge of goethite (α-FeOOH) in freshwaters. Geochim Cosmochim Acta 48:75–80
Toberman H, Evans CD, Freeman C, Fenner N, White M, Emmett BA, Artz RRE (2008) Summer drought effects upon soil and litter extracellular phenol oxidase activity and soluble carbon release in an upland Calluna heathland. Soil Biol Biochem 40:1519–1532
Wang TSC, Li SW (1977) Clay minerals as heterogeneous catalysts in preparation of model humic substances. Z Pfanzenernaehr Bodenkd 140:669–676
Wang K, Xing B (2005) Structural and sorption characteristics of adsorbed humic acid on clay minerals. J Environ Qual 34:342–349
Wang TSC, Li SW, Ferng YL (1978) Catalytic polymerization of phenolic compounds by clay minerals. Soil Sci 126:15–21
Wang TSC, Wang MC, Ferng YL, Huang PM (1983) Catalytic synthesis of humic substances by natural clays, silts and soils. Soil Sci 135:350–360
Wang TSC, Huang PM, Chou CH, Chen JH (1986) The role of soil minerals in the abiotic polymerization of phenolic compounds and formation of humic substances. In: Huang PM, Schnitzer M (eds) Interactions of soil minerals with natural organics and microbes. Soil Science Society of America, Madison, WI, USA, pp 251–281
Wershaw RL (1993) Model for humus in soils and sediments. Environ Sci Technol 27:814–816
Wershaw RL, Pinckney DJ (1980) Isolation and characterization of clay-humic complexes. In: Baker RA (ed) Contaminants and sediments. Ann Arbor Science Publishers, Ann Arbor, Michigan, pp 207–219
Yagudaeva EYu, Muidinov MR, Kapustin DV, Zubov VP (2007) Oxidative polymerization of aniline on the surface of insoluble solid poly(sulfo acids) as a method for the preparation of efficient biosorbents. Russ Chem Bull, Int Edn 56:1166–1173
Zavarzina AG (2006a) A mineral support and biotic catalyst are essential in the formation of highly polymeric soil humic substances. Eurasian Soil Sci 39:48–53
Zavarzina AG (2006b) Key role of mineral support and biotic catalyst in the formation of highly polymeric soil humic acids. In: Proceedings of the 13th meeting of the international humic substances society. Karlsruhe, Germany, July 30–Aug 4 2006, pp 605–608
Zavarzina AG, Semenova TA, Kuznetsova AM, Pogozhev EYu (2007) Synthesis of humic-like substances on the mineral surfaces in presence of oxidases. In: Proceedings International Conference “Humic substances in the biosphere.” Moscow, Dec 19–21, 2007, pp 139–145 (in Russian)
Acknowledgments
The work was supported by the Programme No. 15 of the Presidium of the Russian Academy of Sciences “Origin of the Biosphere and Evolution of Geobiological systems” and Russian Foundation for Fundamental Research grant No. 09-04-00570. The author expresses her sincere gratefulness to Prof. Richard P. Beckett for English revision and to Dr. Alexander A. Lisov for the assistance in preparation of Figs. 10.1, 10.3, and 10.4.
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Zavarzina, A.G. (2010). Heterophase Synthesis of Humic Acids in Soils by Immobilized Phenol Oxidases. In: Shukla, G., Varma, A. (eds) Soil Enzymology. Soil Biology, vol 22. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-14225-3_10
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