EPR investigations of structure of humic acids from compost, soil, peat and soft brown coal upon oxidation and metal uptake

Free radical concentration and theirg-values in humic acids (HA) isolated from various sources were studied by quantitative EPR technique. EPR data for HA formed during composting and natural humification processes occurring in soil, peat and brown coal are given. In more detail the EPR data were analyzed for brown coal HA under carbonization, air oxidation (150°C) as well as metal uptake (Ca(II), Zn(II), Cd(II), Hg(II), Co(II), Ni(II) and Cu(II)) and NO₂ reaction. Two groups of metal complexes were distinguished on the basis of their interaction with free radicals in HA. Ca(II), Zn(II), Cd(II) and Hg(II) ions increase free radical concentration, while Co(II), Ni(II) and Cu(II) ions quench the radicals compared to the raw HA. This phenomenon can be explained either by the strong interaction of the metal ions with active centres responsible for the quinone-hydroquinone-semiquinone equilibria, and/or by the antiferromagnetic interaction between radical spins and metal d orbitals. Gaseous ammonia was found to be a very useful base easily penetrating the solid matrix of HA and strongly influencing the equilibria. β-Diketone groups present in HA react with NO₂ yielding iminoxy radicals. In the HA-metal complexes these structural units are engaged in metal coordination which lowers effectiveness of the iminoxyl synthesis.