Evidence of singlet oxygen and hydroxyl radical formation in aqueous goethite suspension using spin-trapping electron paramagnetic resonance (EPR)

• Published in: Chemosphere (Oxford) 2011-08, Vol.84 (8), p.1095-1101
• Main Authors: Han, Sang Kuk, Hwang, Tae-Mun, Yoon, Yeojoon, Kang, Joon-Wun
• Format: Article
• Language: English
• Subjects: aeration; Applied sciences; Cyclic N-Oxides - chemistry; Electron paramagnetic resonance; electron paramagnetic resonance spectroscopy; Electron Spin Resonance Spectroscopy; Environmental Restoration and Remediation; EPR; Exact sciences and technology; free radical scavengers; Free Radical Scavengers - chemistry; fulvic acids; Goethite; Hydrogen peroxide; Hydroxyl Radical - chemistry; Hydroxyl radicals; Iron Compounds - chemistry; Light; Mannitol; Mathematical analysis; Minerals - chemistry; OH radicals; Oxidation-Reduction; Piperidines - chemistry; Pollution; Radicals; Scavengers; Singlet oxygen; Singlet Oxygen - chemistry; sodium azide; Sodium azides; Soil Pollutants - chemistry; Suspensions - chemistry; traps; Water - chemistry
• ISSN: 0045-6535; 1879-1298
• DOI: 10.1016/j.chemosphere.2011.04.051

► DMPO is used for the detection of OH in the goethite suspended solution (DMPO-OH). ► DMPO-OH could also be formed by the reaction path of singlet oxygen with DMPO. ► In the goethite/H 2O 2 system, DMPO-OH formation have resulted from singlet oxygen. ► DMPO-OH should be carefully calculated by correcting for the amount singlet oxygen. ► Goethite suspensions may act to form singlet oxygen in aqueous environment systems. The generation of reactive species in an aqueous goethite suspension, under room light and aeration conditions, was investigated using the electron paramagnetic resonance (EPR) technique employing spin trap agents. The trap reagents, including 5,5-dimethylpyrroline N-oxide (DMPO) and 2,2,6,6-tetramethylpiperidine (TEMP), were used for the detection of OH radicals (OH ) and singlet oxygen ( 1O 2), respectively. On the addition of DMPO to the goethite suspended solution, a DMPO-OH adduct was formed, which was not decreased, even in the presence of the OH scavenger, mannitol. This result implied a false positive interpretation from the DMPO-OH EPR signal. In the presence of TEMP reagent, a TEMP-O signal was detected, which was completely inhibited in the presence of the singlet oxygen scavenger, sodium azide. With both DMPO-OH and TEMP-O radicals in the presence and absence of radical scavengers, singlet oxygen was observed to be the key species formed in the room-light sensitized goethite suspension. In the goethite/H 2O 2 system; however, both OH and singlet oxygen were generated, with significant portions of DMPO-OH resulting from both OH and singlet oxygen. In fact, the DMPO-OH resulting from OH should be carefully calculated by correcting for the amount of DMPO-OH due to singlet oxygen. This study reports, for the first time, that the goethite suspensions may also act as a natural sensitizer, such as fulvic acids, to form singlet oxygen.