Co-polymerization of penta-halogenated phenols in humic substances by catalytic oxidation using biomimetic catalysis

INTRODUCTION: A synthetic water-soluble meso-tetra(2,6-dichloro-3-sulfonatophenyl)porphyrinate of iron(III) chloride, Fe-(TDCPPS)Cl, was employed to catalyze the oxidative co-polymerization of penta-halogenated phenols in two humic materials of different origin. MATERIALS AND METHODS: Co-polymerization of pentachlorophenol (PCP) was followed by high-performance size-exclusion chromatography (HPSEC), the unbound PCP recovered from reacting humic solutions was evaluated by gas-chromatography/electron capture detector, and the oxidative catalyzed coupling of pentafluorophenol (PFP) into humic matter was assessed by liquid-state 19F-NMR spectroscopy. HPSEC showed that the catalyzed oxidative coupling between PCP and humic molecules increased the apparent weight-average molecular weight (M w) values in both humic substances. RESULTS AND DISCUSSION: HPSEC further indicated that the co-polymerization reaction turned the loosely bound humic supramolecular structures into more stable conformations, which could no longer be disrupted by the disaggregating effect of acetic acid. The occurrence of covalent linkages established between PCP and humic molecules was also suggested by the very little amount of PCP found free in solution after the catalyzed co-polymerization. 19F-NMR spectroscopy suggested that also PFP could be oxidatively coupled to humic materials. PFP-humic co-polymerization reaction produced 19F-spectra with many more 19F signals and wider chemical shifts spread than for PFP alone or PFP subjected to catalyzed coupling without humic matter. CONCLUSIONS: These findings show that biomimetic iron-porphyrin is an efficient catalyst for the covalent binding of polyhalogenated phenols to humic molecules, thereby suggesting that the co-polymerization reaction may become a useful technology to remediate soils and waters contaminated by polyhalogenated phenols and their analogues.