The photodegradation process of m-cresol (3-methylphenol), induced by Fe(III)-Cit complex, was investigated upon irradiation at 365 nm in natural water. The composition and photochemical properties of Fe(III)-Cit complex were studied by UV-Visible absorption spectrophotometer for optimizing the stoichiometry of the complex and photolysis under irradiation at 365 nm, respectively. A dark investigation of the system was performed before studying the photochemical behavior. The photooxidation efficiencies of m-cresol were dependent on the pH value, optimized at pH 2.86, oxygen, initial concentrations of Fe(III)-Cit complex, and m-cresol. Additionally, to look into the mechanism of m-cresol degradation using Fe(III)-Cit, tertiobutanol alcohol was used as scavenger for hydroxyl radicals and the result suggested that hydroxyl radical attack was the main pathway of m-cresol degradation. Besides, oxygen can enhance the photolysis of Fe(III)-Citrate complex by trapping the electron on the carbon centered radical formed after the photoredox process. Then O2•−formed reacts rapidly leading finally to formation of•OH radical. In absence of oxygen, less reactive species are formed; consequently the disappearance of m-cresol was strongly inhibited. Our work shows that the presence of Fe(III)-Citrate complex could have a considerable impact on the fate of organic pollutant in aquatic environment.
The degradation of phenolic compounds (PC) by Fe(III) aquacomplexes was investigated in homogeneous phase at neutral pH in dark and using monochromatic irradiation lamp (365 nm). The process of degradation depends essentially on the concentration of monomeric species, which is the most reactive species in terms of HO• radicals formation. A dark study of a system containing a mixture of phenolic compounds (3,5-dimethylphenol, 2,6-dimethylphenol, m-methylphenol, phenol) and Fe(III) was performed before starting the photochemical study. In this step only the 2,6-dimethylphenol give a thermal reaction with iron in homogenous solution. Under monochromatic excitation (365 nm), the photodegradation of PC induced by Fe(III) aquacomplexes showed that this process followed pseudo first-order kinetic. We investigate also the effect of initial concentrations of Fe(OH)2+, Fe(III) and the substrate. Tertiobutanol, used as scavenger of (HO•), confirmed that this radical was the main pathway of PC degradation. However the degradation of the 2,6-dimethylphenol in the presence of tertiobutanol, was not slowed completely which confirm that the degradation was a combination of thermal and photochemical reactions.
The photolysis of iron(III) organic complexes in the presence of natural and simulated light was a concern for the role it plays within the environment in terms of producing hydroxyl radicals able to degrade organic products. In the present work, the study focused on two iron(III) organic complexes. The characterization of these complexes by spectrometry allowed to show their stability in environment with a stability constant equal to Log β = 13.13 for the complex Fe(III)-malonate, and Log β = 20.85 for the Fe(III)-malate complex. Photolysis of these complexes was carried out using a lamp at 365 nm at different pHs, and followed by several assay Fe(II), H2O2 and •OH. The complexes present different photo-reactivities, in the case of Fe(III)-malate, the photolysis is favored by the Fenton process and generates hydroxyl radicals, contrarily to Fe(III)-malonate photolysis which generates an oxidizing •CH2COOH radical without formation of H2O2 nor of •OH. The presence of oxygen and the addition of isopropanol and chloroform show different effects on the complex photolysis. Complexes mineralization at natural irradiation was also studied using chemical oxygen demand (COD).
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