Deborde Marie, Rabouan Sylvie, Duguet Jean-Pierre, Legube Bernard
Laboratoire de Chimie de l'Eau et de l'Environnement, UMR CNRS 6008, Ecole Supérieure d'Ingénieurs de Poitiers - 40, avenue du Recteur Pineau, 86022 Poitiers, France.
Environ Sci Technol. 2005 Aug 15;39(16):6086-92. doi: 10.1021/es0501619.
This study investigated aqueous ozone-induced oxidation of six endocrine disruptors (EDs: 4-n-nonylphenol, bisphenol A, 17alpha-ethinylestradiol, 17beta-estradiol, estrone, and estriol). In the first part, ED ozonation kinetics were studied over a pH range of 2.5-10.5 at 20 +/- 2 degrees C and in the presence of tert-butyl alcohol. Under these conditions, for each studied compound, the apparent ozone rates presented minima at acidic pH (pH < 5) and maxima at basic pH (pH > 10). In the second part, to explain this pH dependence, elementary reactions, i.e., reactions of ozone with neutral and ionized ED species, were proposed, and the intrinsic constants of each of them were calculated. The reactivity of ozone with ionized EDs (i.e. 1.06 x 10(9)-6.83 x 10(9) M(-1) s(-1)) was found to be 10(4)-10(5) times higher than with neutral EDs (i.e. 1.68 x 10(4) M(-1) s(-1)-2.21 x 10(5) M(-1) s(-1)). At pH > 5, ozone reacted to the greatest extent with dissociated ED forms. Finally, to assess the potential of ozone for inducing ED oxidation in water treatment conditions, the expected removal rates for each of the studied EDs were determined on the basis of the kinetic study at pH = 7 and 20 +/- 2 degrees C. For all EDs considered, O3 exposures of only approximately 2 x 10(-3) mg min L(-1) were calculated to achieve > or = 95% removal efficiency. The ozonation process could thus highly oxidize the studied EDs under water treatment conditions.
本研究调查了臭氧水溶液对六种内分泌干扰物（EDs：4-正壬基酚、双酚A、17α-乙炔雌二醇、17β-雌二醇、雌酮和雌三醇）的氧化作用。在第一部分中，于20±2℃、pH值范围为2.5至10.5且存在叔丁醇的条件下研究了EDs的臭氧化动力学。在这些条件下，对于每种研究的化合物，表观臭氧反应速率在酸性pH值（pH<5）时呈现最小值，在碱性pH值（pH>10）时呈现最大值。在第二部分中，为解释这种pH依赖性，提出了基本反应，即臭氧与中性和离子化ED物种的反应，并计算了它们各自的本征常数。发现臭氧与离子化EDs的反应活性（即1.06×10⁹ - 6.83×10⁹ M⁻¹ s⁻¹）比与中性EDs的反应活性（即1.68×10⁴ M⁻¹ s⁻¹ - 2.21×10⁵ M⁻¹ s⁻¹）高10⁴ - 10⁵倍。在pH>5时，臭氧与离解的ED形式反应程度最大。最后，为评估臭氧在水处理条件下诱导ED氧化的潜力，根据在pH = 7和20±2℃下的动力学研究确定了每种研究的ED的预期去除率。对于所有考虑的EDs，计算得出仅约2×10⁻³ mg min L⁻¹的臭氧暴露量即可实现≥95%的去除效率。因此，臭氧化过程在水处理条件下可高度氧化所研究的EDs。
