Degradation of 2,4-dichlorophenol by activating persulfate and peroxomonosulfate using micron or nanoscale zero-valent copper

[Display omitted] •The activation of PS and PMS by ZVC and nZVC strongly degraded various contaminants.•PS and PMS accelerated the corrosion of ZVC and nZVC to produce Cu+.•Cu+ activated PS and PMS to produce reactive radicals.•SO4− and OH were mainly responsible for the degradation of various contaminants.•Based on the identified intermediates, the 2,4-DCP degradation pathway was proposed. The ability of persulfate (PS) and peroxymonosulfate (PMS) activated by micron or nanoscale zero-valent copper (ZVC or nZVC) to degrade 2,4-dichlorophenol (2,4-DCP) was quantified under various conditions. Mechanism investigation revealed that PS and PMS accelerated the corrosion of ZVC or nZVC to release Cu+ under acidic conditions. The in-situ generated Cu+ further decomposed PS or PMS to produce SO4− and OH, which then dramatically degraded 2,4-DCP. The kobs for 2,4-DCP removal followed pseudo-first-order kinetics, kobs of ZVC/PMS and nZVC/PMS systems were 10∼30 times greater than these in ZVC/PS and nZVC/PS systems. The nZVC/PMS system was most effective to remove 2,4-DCP which even did better than the nZVI/PMS system, with rate constant values ranging from 0.041 to 1.855min−1. At higher pH ZVC is ineffective, but nZVC can activate PS and PMS to significantly degrade 2,4-DCP at pH up to 7.3. The 2,4-DCP degradation pathway was found to involve dechloridation, dehydrogenation, hydroxylation, ring open and mineralization. 56.7% and 45.3% of TOC removals were respectively obtained in the ZVC/PMS and nZVC/PMS systems within 120min. This study helps to comprehend the application of zero-valent metals in reactive radicals-based oxidation processes and the reactivity of Cu+ as an activator of PS and PMS.