Degradation mechanism and influencing factors of 6PPDQ by the potassium peroxymonosulfate/potassium ferrate（Ⅵ）dual-oxidant system

doi:10.16178/j.issn.0528-9017.20250224

Abstract

Abstract:

This study systematically investigated the degradation mechanism and influencing factors of 6PPDQ by the PMS/Fe（Ⅵ）dual-oxidant system. The results demonstrated that the PMS/Fe（Ⅵ）system exhibited significant synergistic effects in the degradation of 6PPDQ，and the degradation efficiency far surpassed that of individual potassium peroxymonosulfate（PMS）or potassium ferrate（Ⅵ）［Fe（Ⅵ）］ systems. By regulating the molar ratio of PMS to Fe（Ⅵ），pH value，and reaction temperature，the degradation efficiency of 6PPDQ was significantly enhanced. Under the conditions of pH 8， 45 °C，and a 1∶1 molar ratio of PMS to Fe（Ⅵ），98% of 6PPDQ was removed within 30 min.Radical quenching experiments and electron paramagnetic resonance spectroscopy （EPR） analysis revealed that singlet oxygen（¹O₂）and high-valent iron species［Fe（Ⅳ）/Fe（V）］played dominant roles in the degradation process，while the contributions of hydroxyl radical（·OH）were relatively minor. Fe（Ⅵ）exhibited a significant activation effect on PMS. Probe experiments further confirmed that PMS not only generated radicals through self-decomposition but also promoted the formation of high-valent iron species from Fe（Ⅵ），thereby enhancing the oxidative capacity of the system. This study demonstrated the synergistic effect of the PMS/Fe（Ⅵ）system in the degradation of 6PPDQ.

Key words: potassium peroxymonosulfate（PMS）, potassium ferrate（Ⅵ）［Fe（Ⅵ）］, 6PPDQ, synergistic degradation

CLC Number:

YU Haibin, WU Nannan, QI Peipei, GU Chengbo, WANG Xinquan. Degradation mechanism and influencing factors of 6PPDQ by the potassium peroxymonosulfate/potassium ferrate（Ⅵ）dual-oxidant system[J]. Journal of Zhejiang Agricultural Sciences, 2026, 67(10): 2525-2531.

Figures/Tables 8

Table 1 Liquid chromatography detection conditions

有机物	检测波长/nm	流动相种类及比例（体积比）	流速/（mL·min^-1）	柱温/℃	保留时间/min
6PPDQ	360	0.1%甲酸-乙腈，5∶95	1.0	30	4.312
PMSO	230	乙腈-水，20∶80	0.8	30	4.987
PMSO₂	215	乙腈-水，20∶80	0.8	30	7.193

Fig.1 Degradation efficiency of different oxidation systems on 6PPDQ

Fig.2 The effect of oxidant feeding ratios on the degradation efficiency of 6PPDQ

Fig.3 The effect of pH value on the degradation efficiency of 6PPDQ

Fig.4 The effect of temperature on the degradation efficiency of 6PPDQ

Fig.5 The degradation efficiency of the PMS/Fe（Ⅵ）system on 6PPDQ under different quenching agent conditions

Fig.6 EPR spectra of ·OH（a）and 1O?（b）under different systems

Fig.7 Results of the PMSO probe test

References 16

[1]	戴情园，谭弘李，张婧，等. 我国对苯二胺类抗氧化剂及其衍生醌类化合物污染现状及健康风险研究进展［J］. 环境化学，2024，43（10）：3207-3223.
[2]	Tian Z Y， Zhao H Q， Peter K T，et al. A ubiquitous tire rubber-derived chemical induces acute mortality in coho salmon［J］. Science，2021，371（6525）：185-189.
[3]	Hiki K， Asahina K， Kato K，et al. Acute toxicity of a tire rubber-derived chemical，6PPD quinone，to freshwater fish and crustacean species［J］. Environmental Science & Technology Letters，2021，8（9）：779-784.
[4]	Fang L Y， Fang C L， Di S S，et al. Oral exposure to tire rubber-derived contaminant 6PPD and 6PPD-quinone induce hepatotoxicity in mice［J］. Science of the Total Environment，2023，869：161836.
[5]	Di S S， Xu H G， Yu Y D，et al. Environmentally relevant concentrations of S-6PPD-quinone caused more serious hepatotoxicity than R-enantiomer and racemate in Oncorhynchus mykiss ［J］. Environmental Science & Technology，2024，58（40）：17617-17628.
[6]	Wang W， Cao G D， Zhang J，et al. p-phenylenediamine-derived quinones as new contributors to the oxidative potential of fine particulate matter［J］. Environmental Science & Technology Letters，2022，9（9）：712-717.
[7]	Zoroufchi Benis K， Behnami A， Minaei S，et al. Environmental occurrence and toxicity of 6PPD quinone，an emerging tire rubber-derived chemical：a review［J］. Environmental Science & Technology Letters，2023，10（10）：815-823.
[8]	Du B B， Liang B W， Li Y，et al. First report on the occurrence of N-（1，3-dimethylbutyl）-N'- phenyl-p-phenylenediamine（6PPD）and 6PPD-quinone as pervasive pollutants in human urine from south China［J］. Environmental Science & Technology Letters，2022，9（12）：1056-1062.
[9]	Wang W， Cao G D， Zhang J，et al. UV-induced photodegradation of emerging para-phenylenediamine quinones in aqueous environment：kinetics，products identification and toxicity assessments［J］. Journal of Hazardous Materials，2024，465：133427.
[10]	Foscari A， Seiwert B， Zahn D，et al. Leaching of tire particles and simultaneous biodegradation of leachables［J］. Water Research，2024，253：121322.
[11]	Jiao M， Luo Y W， Zhang F，et al. Transformation of 6PPDQ during disinfection：kinetics，products，and eco-toxicity assessment［J］. Water Research，2024，250：121070.
[12]	Chen L， Hu J R， Borthwick A G L，et al. Solar-light-activated periodate for degradation and detoxification of highly toxic 6PPD-quinone at environmental levels［J］. Nature Water，2024，2（5）：453-463.
[13]	Feng M B， Cizmas L， Wang Z Y，et al. Synergistic effect of aqueous removal of fluoroquinolones by a combined use of peroxymonosulfate and ferrate（Ⅵ）［J］. Chemosphere，2017，177：144-148.
[14]	Ji F， Li C L， Wei X Y. Efficient performance of porous Fe₂O₃ in heterogeneous activation of peroxymonosulfate for decolorization of Rhodamine B［J］. Chemical Engineering Journal，2013，231：434-440.
[15]	Zhang X J， Zhu X B， Li H，et al. Combination of peroxymonosulfate and Fe（Ⅵ）for enhanced degradation of sulfamethoxazole：the overlooked roles of high-valent iron species［J］. Chemical Engineering Journal，2023，453：139742.
[16]	Wang Z， Qiu W， Pang S Y，et al. Relative contribution of ferryl ion species（Fe（Ⅳ））and sulfate radical formed in nanoscale zero valent iron activated peroxydisulfate and peroxymonosulfate processes［J］. Water Research，2020，172：115504.