Superoxide anion radical generation in the NaOH/H(2)O(2)/Fe(III) system: a spin trapping ESR study.

Formation of free radical intermediates in a NaOH/H(2)O(2)/Fe(III) system has been studied by ESR spectroscopy in the presence of the spin trap 5,5-dimethy-1-pyrroline N-oxide (DMPO). DMPO/O(2(*) ) (-) and DMPO/(*)OH signals were simultaneously detected in this system, but only the DMPO/(*)OH signal could be observed in the absence of Fe(III). Effects of pH values and Fe(III) concentrations on the ESR signal intensities were investigated in detail. Formation of DMPO/O(2(*) ) (-) adduct was inhibited by the addition of superoxide dismutase (SOD), catalase or nitro blue tetrazolium (NBT), and by chelating the Fe(III) with some chelators, including ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and desferrioxamine (DFO). Deoxygenation from the NaOH/H(2)O(2)/Fe(III) mixture had a slight effect on the formation of DMPO/O(2(*) ) (-). DMPO/O(2(*) ) (-) signal was also detected from the NaOH/H(2)O(2)/Fe(II) mixture, but it can be totally suppressed under anaerobic conditions. Considering the hydrolysis of Fe(III) into polymerization iron species with oxide phases in the alkaline medium, Fe(2)O(3) was directly suspended into a mixture of NaOH/H(2)O(2) for comparison. Fortunately, the presence of Fe(2)O(3) suspension was found to be of benefit to the production of DMPO/O(2(*) ) (-). Influence of aging time of hydrolytic iron species on the superoxide anion radical generation was also studied. These results suggest that the generation of O(2(*) ) (-) from the NaOH/H(2)O(2)/Fe(III) system was probably caused by the heterogeneous surface catalysis initiated by hydrolytic iron species.