Oxidation of phenolic endocrine disrupting chemicals by potassium permanganate in synthetic and real waters.
In this study, five selected environmentally relevant phenolic endocrine disrupting chemicals (EDCs),  estrone, 17β-estradiol, estriol, 17α-ethinylestradiol, and 4-n-nonylphenol, were shown to exhibit similarly appreciable reactivity toward potassium permanganate [Mn(VII)] with a second-order rate constant at near neutral pH comparable to those of ferrate(VI) and chlorine but much lower than that of ozone. In comparison with these oxidants, however, Mn(VII) was much more effective for the oxidative removal of these EDCs in real waters, mainly due to the relatively high stability of Mn(VII) therein. Mn(VII) concentrations at low micromolar range were determined by an ABTS [2,2-azino-bis(3-ethylbenzothiazoline)-6-sulfonic acid diammonium] spectrophotometric method based on the stoichiometric reaction of Mn(VII) with ABTS [Mn(VII) + 5ABTS → Mn(II) + 5ABTS(•+)] forming a stable green radical cation (ABTS(•+)). Identification of oxidation products suggested the initial attack of Mn(VII) at the hydroxyl group in the aromatic ring of EDCs, leading to a series of quinone-like and ring-opening products. The background matrices of real waters as well as selected model ligands including phosphate, pyrophosphate, NTA, and humic acid were found to accelerate the oxidation dynamics of these EDCs by Mn(VII). This was explained by the effect of in situ formed dissolved Mn(III), which could readily oxidize these EDCs but would disproportionate spontaneously without stabilizing agents.
State Key Laboratory of Urban Water Resource and Environment, School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090, China.
Jin
J
Jiang
Su-Yan
SY
Pang
Jun
J
Ma
Huiling
H
Liu
D052160:Benzothiazoles; D052244:Endocrine Disruptors / Q000737:chemistry*; D007202:Indicators and Reagents; D007700:Kinetics; D010084:Oxidation-Reduction; D010636:Phenols / Q000737:chemistry*; D011196:Potassium Permanganate / Q000737:chemistry*; D013057:Spectrum Analysis / Q000379:methods; D013451:Sulfonic Acids; D014865:Waste Disposal, Fluid / Q000379:methods*; D014874:Water Pollutants, Chemical / Q000737:chemistry*; D018508:Water Purification / Q000379:methods*
D052160:Benzothiazoles; D052244:Endocrine Disruptors; D007202:Indicators and Reagents; D010636:Phenols; D013451:Sulfonic Acids; D014874:Water Pollutants, Chemical; D011196:Potassium Permanganate; C002502:2,2'-azino-di-(3-ethylbenzothiazoline)-6-sulfonic acid