Phosphate-mediated degradation of organic pollutants in water with peroxymonosulfate revisited: Radical or non-radical oxidation?

Whilst it is generally recognized that phosphate enables to promote the removal of some organic pollutants with peroxymonosulfate (PMS) oxidation, however, there is an ongoing debate as to whether free radicals are involved. By integrating different methodologies, here we provide new insights into the reaction mechanism of the binary mixture of phosphates (i.e., NaH2PO4, Na2HPO3, and NaH2PO2) with peroxymonosulfate (PMS) or hydrogen peroxide (H2O2). Enhanced degradation of organic pollutants and observation of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) adducts (i.e. DMPOOH and 5,5-dimethyl-2-oxopyrroline-1-oxyl (DMPOX)) with electron paramagnetic resonance (EPR) in most phosphates/PMS system seemly support a radical-dominant mechanism. However, fluorescence probe experiments confirm that no significant amount of hydroxyl radicals (•OH) are produced in such reaction systems. PMS in the phosphate solutions (without any organics) remains relatively stable, but is only consumed while organic substrates are present, which is distinct from a typical radical-dominant Co2+/PMS system where PMS is continuously decomposed. Through density functional theory (DFT) calculation, the energy barriers of the phosphates/PMS reaction processes are greatly decreased when non-radical mechanism dominates. Complementary evidence suggests that the reactive intermediates of PMS-phosphate complex, rather than the free radicals, are capable of oxidizing electron-rich substrates such as DMPO and organic pollutants. Taking the case of phosphate/PMS system as an example, this study demonstrates the necessity of acquisition of lines of evidence for resolving paradoxes in identifying EPR adducts.

Application of persulfate-based oxidation processes to address diverse sustainability challenges: A critical review.

Over the past years, persulfate (PS) is widely applied due to their high versatility and efficacy in decontamination and sterilization. While treatment of organic chemicals, remediation of soil and groundwater, sludge treatment, disinfection on pathogen microorganisms have been covered by most published reviews, there are no comprehensive and specific reviews on its application to address diverse sustainability challenges, including solid waste treatment, resources recovery and regeneration of ecomaterials. PS applications mainly rely on direct oxidation by PS itself or the reactive sulfate radical (SO4•-) or hydroxyl radical (•OH) from the activation of peroxodisulfate (PDS, S2O82-) or peroxymonosulfate (PMS, HSO5-) in SO4•--based advanced oxidation processes (SO4•--AOPs). From a broader perspective of environmental cleanup and sustainability, this review summarizes the various applications of PS except pollutant decontamination and elaborates the possible reaction mechanisms. Additionally, the differences between PS treatment and conventional technologies are highlighted. Challenges, research needs and future prospect are thus discussed to promote the development of the applications of PS-based oxidation processes in niche environmental fields. In all, this review is a call to pay more attention to the possibilities of PS application in practical resource reutilization and environmental protection except widely reported pollutant degradation.