State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai, China.
State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai, China; China Academy of Urban Planning & Design, Beijing, China.
Chemosphere. 2018 Feb;193:602-610. doi: 10.1016/j.chemosphere.2017.11.075. Epub 2017 Nov 16.
Degradation of diethyl phthalate (DEP) by ultraviolet/persulfate (UV/PS) process at different reaction conditions was evaluated. DEP can be degraded effectively via this process. Both tert-butyl (TBA) and methanol (MeOH) inhibited the degradation of DEP with MeOH having a stronger impact than TBA, suggesting sulfate radical () and hydroxyl radical (HO) both existed in the reaction systems studied. The second-order rate constants of DEP reacting with and HO were calculated to be (6.4±0.3)×10 Ms and (3.7±0.1)×10 Ms, respectively. To further access the potential degradation mechanism in this system, the pseudo-first-order rate constants (k) and the radical contributions were modeled using a simple steady-state kinetic model involving and HO. Generally, HO had a greater contribution to DEP degradation than . The k of DEP increased as PS dosages increased when PS dosages were below 1.9 mM. However, it decreased with increasing initial DEP concentrations, which might be due to the radical scavenging effect of DEP. The k values in acidic conditions were higher than those in alkaline solutions, which was probably caused by the increasing concentration of hydrogen phosphate (with higher scavenging effects than dihydrogen phosphate) from the phosphate buffer as pH values rose. Natural organic matter and bicarbonate dramatically suppressed the degradation of DEP by scavenging and HO. Additionally, the presence of chloride ion (Cl) promoted the degradation of DEP at low Cl concentrations (0.25-1 mM). Finally, the proposed degradation pathways were illustrated.
评估了不同反应条件下紫外/过硫酸盐(UV/PS)工艺对邻苯二甲酸二乙酯(DEP)的降解情况。通过该工艺可有效降解 DEP。叔丁醇(TBA)和甲醇(MeOH)均抑制了 DEP 的降解,其中 MeOH 的抑制作用强于 TBA,表明反应体系中同时存在硫酸根自由基()和羟基自由基(HO)。计算得出 DEP 与 HO 反应的二级速率常数分别为(6.4±0.3)×10 M-1s-1和(3.7±0.1)×10 M-1s-1。为进一步探究该体系中的潜在降解机制,采用包含和 HO 的简单稳态动力学模型对假一级速率常数(k)和自由基贡献进行建模。通常,HO 对 DEP 降解的贡献大于。当 PS 剂量低于 1.9 mM 时,随着 PS 剂量的增加,DEP 的 k 值增加。然而,随着初始 DEP 浓度的增加,k 值降低,这可能是由于 DEP 的自由基清除效应。在酸性条件下的 k 值高于碱性溶液中的 k 值,这可能是由于磷酸盐缓冲液中随着 pH 值的升高,磷酸氢盐(比磷酸二氢盐具有更高的清除作用)的浓度增加所致。天然有机物和碳酸氢根通过清除和 HO 极大地抑制了 DEP 的降解。此外,在低浓度 Cl(0.25-1 mM)存在下,Cl 促进了 DEP 的降解。最后,提出了降解途径。