Complexation reactions with humic substances

The adsorption-desorption reaction in Eq. 4.3 has been applied to soils in an average sense in a spirit very similar to that of the complexation reactions for humic substances, discussed in Section 2.3.11 Although no assumption of uniformity is made, the use of Eq. 4.3 to describe adsorption or desorption processes in chemically heterogeneous porous media such as soils does entail the hypothesis that effective or average equilibrium (or rate) constants provide a useful representation of a system that in reality exhibits a broad spectrum of surface reactivity. This hypothesis will be an adequate approximation so long as this spectrum is unimodal and not too broad. If the spectrum of reactivity is instead multimodal, discrete sets of average equilibrium or rate constants—each connected with its own version of Eq. 4.3—must be invoked and if the spectrum is very broad, the sets of these parameters will blend into a continuum (cf. the affinity spectrum in Eq. 2.38). 

The study of Lovgren et al. (1987) provides an example of the application of a discrete functional group approach to model the complexation of aluminium with humic substances found in bog-water. The acid-base titration behaviour of the humic material found in Swedish bog-water was modelled as a diprotic acid with the following reactions and acid dissociation constants ... 

The first involves a known functional group derivatization to quantify specific types of carbons found in humic substances, the derivatization being carried out by chemical reactions with l C-labeled reactants.( d-27) For example, methylation with C-labeled diazomethane or methyl iodide has been used to distinguish between and quantify hydroxyl functionalities in humic acids. The second labeling methodology involves the use of C-labeled reactants to follow the course of a complex reaction or association such as the interaction of pollutants with humic acids.(6-9,22,2J) The first structural evidence for the type of interaction of pollutants with humic substances was provided using and site specific labeling in combination with and NMR, respectively. 

MnP is the most commonly widespread of the class II peroxidases [72, 73], It catalyzes a PLC -dependent oxidation of Mn2+ to Mn3+. The catalytic cycle is initiated by binding of H2O2 or an organic peroxide to the native ferric enzyme and formation of an iron-peroxide complex the Mn3+ ions finally produced after subsequent electron transfers are stabilized via chelation with organic acids like oxalate, malonate, malate, tartrate or lactate [74], The chelates of Mn3+ with carboxylic acids cause one-electron oxidation of various substrates thus, chelates and carboxylic acids can react with each other to form alkyl radicals, which after several reactions result in the production of other radicals. These final radicals are the source of autocataly tic ally produced peroxides and are used by MnP in the absence of H2O2. The versatile oxidative capacity of MnP is apparently due to the chelated Mn3+ ions, which act as diffusible redox-mediator and attacking, non-specifically, phenolic compounds such as biopolymers, milled wood, humic substances and several xenobiotics [72, 75, 76]. 

The toxin is also likely to be adsorbed or complexed by soil humic acids. If the reaction is a simple adsorption reaction, all or part of the toxin might later become available for absorption by a receiver plant. If the toxin is complexed or precipitated by its reaction with soil humic substances, then it would be deactivated. 

FIGURE 6 Potential interactive pathways and processes of humic substances emanating from decomposition products of higher plant tissues with extracellular and surface-bound enzymes and photolytic reactions, particularly with UV irradiance. Humic acid-enzyme complexes can be stable for long periods (weeks and months) and subsequently reactivated upon exposure to weak UV light. Further photolysis can cleave simple compounds from the macromolecules for subsequent utilization by microbes. 

Lu, X.Q. and Johnson, W.D. (1997) The reaction of aquatic humic substances with cop-per(II) ions an ESR study of complexation. Sci. Total Environ., 203, 199-207. Lugtenberg, B. and van Alphen, L. (1983) Molecular architecture and functioning of the outer membrane of Escherichia coli and other Gram-negative bacteria. Biochim. Biophys. Acta, Til, 51-115. 

In addition to its relative simplicity, the quasiparticle approach has the advantage of a formal mathematical structure that is analogous to that described in Section 2.1 for complexes involving nonpolymeric ligands, such as F or C2O4. Thus, for example, the complexation reaction between Al3+ and a humic substance Scatchard quasiparticle, L, can be written by analogy with Eq. 2.5a ... 

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