Oxidative degradation of chlorophenolic compounds with pyrite-Fenton process

Batch experiments, in conjunction with chromatographic and spectroscopic measurements, were performed to comparatively investigate the degradation of various chlorophenolic (CP) compounds (e.g., 2-CP, 4-CP, 2,3-DCP, 2,4-DCP, 2,4,6-TCP, 2,3,4,6-TeCP) by a modified Fenton process using pyrite as the catalyst. The batch results show that the CP removal by pyrite-Fenton process was highly dependent on chemical conditions (e.g., pH, CP and pyrite concentration), CP type, number and location of chlorine atoms on the aromatic ring. With the exception of 2,3,4,6-TeCP and 2,3-DCP, the CP removal decreased with increasing the number of chlorine constituents. While the main mechanism responsible for monochlorophenol removal (e.g., 2-CP and 4-CP) was the hydroxyl radical attack on aromatic rings, the CP removal for multichlorophenolic compounds (e.g., 2,3,4,6-TeCP) was driven by both: (1) hydroxyl radical attack on aromatic rings by both solution and surface-bound hydroxyl radicals and (2) adsorption onto pyrite surface sites. The adsorption affinity increased with increasing the number of Cl atoms on the aromatic ring due to enhanced hydrophobic effect. The TOC removal was not 100% complete for all CPs investigated due to formation of chemically less degradable chlorinated intermediate organic compounds as well as low molecular weight organic acids such as formic and acetic acid. Spectroscopic measurements with SEM-EDS, zeta potential and XPS provided evidence for the partial oxidation of pyrite surface Fe(II) and disulfide groups under acidic conditions.