Activation of peroxymonosulfate by base for degradation of methylene blue: role of bromide ions.

Abstract

Bromide ions are inevitable in aquatic environment and influence the degradation of contaminants in non-radical based advanced oxidation processes, but the role of reactive bromine species (RBS) remain obscure. This study investigated the role of bromide ions in the degradation of methylene blue (MB) during the base/peroxymonosulfate (PMS) process. The formation of RBS as a function of bromide ions were evaluated using a kinetic modelling. Bromide ions were shown to play crucial roles in MB degradation. Increasing the dosage of NaOH and Br- increased the transformation kinetics of MB. However, brominated intermediates which are more toxic than precursor MB were generated in the presence of Br-. The formation of adsorbable organic halides (AOX) was enhanced by elevating the dosage of Br-. The formation of AOX was even more significant in the absence of NaOH, and the AOX values decreased with the increasing alkalinity. The kinetic model indicated that the dominant reactive species formed in the base/PMS/Br- process are 1O2 and HOBr, and Br2 in the Br-/PMS process. Therefore, the influence of bromide ions should be taken into consideration in the application of the base/PMS process for organic matters in bromide-containing natural water. Strategies should be developed to make full use of RBS for the abatement of organic pollutants and to reduce the formation of AOX. This study reveals that in the treatment of saline wastewater by PMS-based processes, increasing the amount of NaOH may be an effective strategy to inhibit the accumulation of AOX.