Ying Liwen, Dong Wenbo, Yuan Haixia, Liu Yan, Ma Luming
Department of Environmental Science and Engineering, Fudan University, Shanghai, 200433, China.
Environ Sci Pollut Res Int. 2015 Jun;22(11):8507-16. doi: 10.1007/s11356-014-3995-0. Epub 2014 Dec 30.
Br(-) and nitrogen-containing organic pollutants, such as amino acids, protein, etc., were often detected in water and wastewater treatment plants using advanced oxidation technologies. All these technologies have one common characteristic, that is, the removal processes involve ·OH. Therefore, it is necessary to study the different reaction pathways among ·OH, Br(-), and amino acids. In this research, glycine was chosen as the representative of amino acids and H2O2 was selected as ·OH precursor. Results showed that Br(-) had a shielding effect on [Formula: see text] of α-carbon in glycine, when it was abstracted by ·OH. The main reaction pathway in the system containing Br(-) was the abstraction of H from amino group in glycine by ·OH, contributing 85 % of total abstracted H. This system had a prominent phenomenon of decarboxylation and performed as alkali production dominating. However, in the system not containing Br(-), the main reaction pathway was the abstraction of H from α-carbon in glycine by ·OH, contributing 97 % of total abstracted H. This system performed as acid production dominating. By laser flash photolysis, the second-order rate constants of abstraction of H from both α-carbon and amino group in glycine by ·OH were obtained as (3.3 ± 0.5) × 10(7) M(-1)·s(-1) and (8.2 ± 0.8) × 10(8) M(-1)·s(-1), respectively. The second-order rate constants of the reaction between [Formula: see text], HṄCH2COO(-) and H2O2 were (1.5 ± 1.1) × 10(7) M(-1)·s(-1) and (4.4 ± 0.3) × 10(7) M(-1)·s(-1), respectively. In addition, Br(-) was found to play a catalytic role in the decomposition of H2O2 under UV radiation. The results mentioned above were significant for the application of advanced oxidation technologies for water containing both amino acids and Br(-) in water and wastewater treatment plants.
在采用高级氧化技术的自来水厂和污水处理厂中,经常检测到溴离子(Br(-))以及含氮有机污染物,如氨基酸、蛋白质等。所有这些技术都有一个共同特点,即去除过程都涉及·OH。因此,有必要研究·OH、Br(-)和氨基酸之间不同的反应路径。本研究选用甘氨酸作为氨基酸的代表,选择过氧化氢(H2O2)作为·OH的前体。结果表明,当甘氨酸α-碳上的氢被·OH提取时,Br(-)对其具有屏蔽作用。含Br(-)体系中的主要反应路径是·OH提取甘氨酸氨基上的氢,占提取氢总量的85%。该体系有显著的脱羧现象,且以产碱为主。然而,在不含Br(-)的体系中,主要反应路径是·OH提取甘氨酸α-碳上的氢,占提取氢总量的97%。该体系以产酸为主。通过激光闪光光解,得到·OH提取甘氨酸α-碳和氨基上氢的二级速率常数分别为(3.3±0.5)×10(7) M(-1)·s(-1)和(8.2±0.8)×10(8) M(-1)·s(-1)。[具体化学式]、HṄCH2COO(-)与H2O2反应的二级速率常数分别为(1.5±1.1)×10(7) M(-1)·s(-1)和(4.4±0.3)×10(7) M(-1)·s(-1)。此外,发现Br(-)在紫外辐射下对H2O2的分解起催化作用。上述结果对于自来水厂和污水处理厂中含氨基酸和Br(-)的水采用高级氧化技术具有重要意义。