Ruixia Yuan

Effects of chloride ion on degradation of Acid Orange 7 by sulfate radical-based advanced oxidation process: implications for formation of chlorinated aromatic compounds

Sodium chloride is a common salt used during textile wet processes. Here a dual effect of chloride (i.e. inhibitory and accelerating effect) on azo dye (Acid Orange 7, AO7) degradation in an emerging cobalt/peroxymonosulfate (Co/PMS) advanced oxidation process (AOP) was reported. Compared to OH-based AOPs, high concentrations of chloride (>5mM) can significantly enhance dye decoloration independent of the presence of the Co(2+) catalyst, but did greatly inhibit dye mineralization to an extent which was closely dependent upon the chloride content. Both UV-vis absorbance spectra and AOX determination indicated the formation of some refractory byproducts. Some chlorinated aromatic compounds, including 3-chloroisocoumain, 2-chloro-7-hydroxynaphthalene, 1,3,5-trichloro-2-nitrobenzene and tetrachlorohydroquione, were identified by GC-MS measurement in both Co/PMS/Cl(-) and PMS/Cl(-) reaction systems. Based on those experimental results, two possible branched (SO(4)(-)radical-based and non-radical) reaction pathways are proposed. This is one of the very few studies dealing with chlorinated organic intermediates formed via chlorine radical/active chlorine species (HOCl/Cl(2)) attack on dye compounds. Therefore, this finding may have significant technical implications for utilizing Co/PMS regent to detoxify chloride-rich azo dyes wastewater.

Effects of chloride ions on bleaching of azo dyes by Co2+/Oxone regent: kinetic analysis

Orange II (Org II), one of the most common used azo dyes, was taken as a model to investigate the effects of chloride ion on dye decoloration in cobalt/peroxymonosulfate (Co/PMS) system. A significant decrease in the rate of Org II decoloration was observed upon addition of Cl(-) (0.05-10mM), but further addition of Cl(-) (>50mM) apparently accelerated dyes degradation. This dual effect of chloride on dyes bleaching was also observed as other halide ions (e.g. Br(-), I(-)) or other azo dyes were present in Co/PMS system. In the Co-free PMS solutions, the observed first-order rate constant always exponentially increased with the chloride content. The reactive chlorine species generated from chloride oxidation by PMS should be responsible for this non-radical mechanism for dye decoloration, however, these rapid decoloration of Org II as chloride ion was present, did not readily lead to much mineralization. Therefore, this finding may have significant technical implications for utilizing Co/PMS regent to detoxify chloride-rich azo dyes wastewater.

Deciphering the degradation/chlorination mechanisms of maleic acid in the Fe(II)/peroxymonosulfate process: An often overlooked effect of chloride

In recent years, a significant effort has been devoted into investigating the effects of chloride on the degradation kinetics of aromatic pollutants. The impact of chloride on the decomposition of short-chain carboxylic acid intermediates from aromatics degradation has often been overlooked. In this study the roles of chloride in the oxidation of maleic acid (MA) in the Fe(II)/peroxymonosulfate (PMS) process was investigated. Degradation efficiency, reaction intermediates, adsorbable organic halogen (AOX) accumulation and mineralization were examined. The chloride ion (Cl-) was found to have an overall negative impact on MA degradation and mineralization in the Fe(II)/PMS system. The presence of Cl- led to the formation of chlorinated by-products and a high production of AOX. The mineralization of MA was decreased with increasing Cl- concentrations. Kinetic modeling demonstrated the impact of various radicals largely depended on the concentration of Cl-. The significance of Cl2•- or Cl2 for MA destruction was enhanced with increasing Cl- content, and overwhelmed that of SO4•- when the Cl- concentration was over 5 mM. In the absence of Cl-, SO4•- was the primary radical responsible for MA oxidation. A possible degradation pathway is proposed (cis-trans isomerization, decarboxylation and halogenations processes). These results may help to understand the full oxidation pathways of refractory aromatic compounds and the mechanism of chlorinated by-products formation in industrial saline wastewater treatment.