Kinetics, Degradation Pathways, Toxicity Changes, and Disinfection By-Product Formation in Degradation of Nabumetone by UV/Monochloramine Advanced Oxidation Processes
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摘要: 紫外活化氯胺高级氧化工艺对降解有机微污染物具有潜在应用价值. 为探究紫外/一氯胺(UV/NH2Cl)工艺对水中非甾体抗炎药的去除性能，选用萘丁美酮(nabumetone, NMT)为降解对象，比较UV光解、NH2Cl氧化和UV/NH2Cl这3种手段对NMT的降解性能，考察NH2Cl投加量、pH、Cl−、HCO3−和天然有机物(natural organic matters, NOM)对UV/NH2Cl降解NMT的影响，结合量子化学计算和UPLC-HRMS检测结果探究NMT的降解路径并预测毒性变化，最后分析消毒副产物的生成情况. 结果表明：①UV/NH2Cl体系内NMT的降解过程符合拟一级反应动力学方程，在温度25 ℃、NMT初始浓度5 μmol/L、NH2Cl投加量50 μmol/L的条件下，反应150 s后NMT的降解效率可达88.81%. ②增加NH2Cl投加量可促进NMT降解，pH在5.5~8.5范围内对NMT降解速率无明显变化，Cl−、HCO3−和NOM对NMT的降解具有抑制作用. ③基于UPLC-HRMS共鉴定出10种降解产物，NMT降解过程主要涉及羟基化、亚硝基化和去甲基化等反应，TEST软件预测表明，降解产物的急性毒性和发育毒性比NMT母体更高. ④气相色谱检测结果显示，UV/NH2Cl促进了NMT降解过程中消毒副产物的产生. 研究显示，UV/NH2Cl高级氧化工艺对水中NMT具有良好的降解效能，其降解产物可能存在更高的急性毒性和发育毒性，后续需进一步探究.
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关键词:
- 紫外/一氯胺(UV/NH2Cl) /
- 萘丁美酮(NMT) /
- 动力学 /
- 降解路径 /
- 消毒副产物
Abstract: UV-activated chloramine advanced oxidation process has potential application value in the degradation organic micropollutants. In order to investigate the removal performance of non-steroidal anti-inflammatory drugs in water by ultraviolet/monochloramine (UV/NH2Cl) system, the degradation of nabumetone (NMT) by UV photolysis, NH2Cl oxidation and UV/NH2Cl was compared. The influence of various factors on the degradation of NMT by UV/NH2Cl was investigated. The degradation pathways of NMT was investigated and the toxicity changes were predicted by combining the quantum chemical calculation and the detection results of UPLC-HRMS. Finally, the generation of disinfection by-products was analyzed. The results show that: (1) The degradation of NMT in UV/NH2Cl system conforms to the pseudo-first-order reaction kinetics equation. Under the conditions of 25 ℃, the initial concentration of NMT is 5 μmol/L, and the dosage of NH2Cl is 50 μmol/L, the degradation efficiency of NMT could reach 88.81% after 150 s of reaction. (2) Increasing the dose of NH2Cl can promote the degradation of NMT, and there is no significant change in the degradation rate of NMT in the range of pH 5.5-8.5. Cl−, HCO3−and natural organic matter inhibit the degradation of NMT. (3) A total of 10 degradation products were identified based on UPLC-HRMS, and the degradation process of NMT mainly involved hydroxylation, nitrosation and demethylation. The TEST software predicted that, The acute and developmental toxicity of the degradation products were higher than that of the NMT. (4) Gas chromatography analysis results showed that UV/NH2Cl promoted the generation of disinfection byproducts during the degradation of NMT. The results of this study show that UV/NH2Cl advanced oxidation process has good degradation efficiency for NMT in water, and its degradation products may have higher acute and developmental toxicity, which needs further investigation. -
图 1 UV/NH2Cl体系内主要自由基的产生路径
Figure 1. Main radical formation pathways in the UV/NH2Cl system
图 2 不同降解手段对NMT的降解效能
Figure 2. Degradation efficiency of NMT by different degradation method
图 3 NH2Cl投加量对UV/NH2Cl降解NMT的影响
Figure 3. Effects of NH2Cl dosage on degradation of NMT by UV/NH2Cl
图 4 溶液初始pH对UV/NH2Cl降解NMT的影响
Figure 4. Effects of solution pH on degradation of NMT by UV/NH2Cl
图 5 Cl−浓度对UV/NH2Cl降解NMT的影响
Figure 5. Effects of Cl− concentration on degradation of NMT by UV/NH2Cl
图 6 HCO3−浓度对UV/NH2Cl降解NMT的影响
Figure 6. Effects of HCO3− concentration on degradation of NMT by UV/NH2Cl
图 7 NOM浓度对UV/NH2Cl降解NMT的影响
Figure 7. Effects of NOM concentration on degradation of NMT by UV/NH2Cl
图 8 优化后的NMT分子几何构型
注：1～32表示原子编号，灰色表示C原子，红色的表示O原子.
Figure 8. The optimized geometric configuration of NMT molecular
图 11 UV/NH2Cl处理NMT的可能降解路径
Figure 11. Proposed NMT degradation pathways by UV/NH2Cl treatment
图 12 UV/NH2Cl降解NMT过程的毒性变化
Figure 12. Toxicity changes during the degradation process of NMT by UV/NH2Cl
图 13 UV/NH2Cl降解NMT消毒副产物的生成浓度
Figure 13. Concentration of DBPs during the degradation process of NMT by UV/NH2Cl
表 1 超高效液相色谱梯度洗脱
Table 1. Gradient elution of UPLC
时间/min 流动相组成 流速/(mL/min) 0~10 20%~80% A相，80%~20% B相 0.25 14~14.1 80%~20% A相，20%~80% B相 0.25 14.1~20 20% A相，80% B相 0.25 
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表 2 不同降解手段对NMT的降解速率常数
Table 2. Degradation rate constant of NMT in different methods
降解手段 kobs/s−1 R2 单独UV光解 2.18 × 10−5 0.983 单独NH2Cl氧化 1.13 × 10−4 0.997 UV/NH2Cl 1.43 × 10−2 0.998
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表 3 NMT的自然布局分析(NPA)电荷分布和福井函数
Table 3. Ntural population analysis (NPA) charge distribution and Fukui index of NMT
原子 电荷(0) e/Å 电荷(−1) e/Å 电荷(+1) e/Å f+ f− f0 C1 0.068 5 0.032 5 0.128 0 0.059 6 0.036 0 0.047 8 C2 −0.037 9 −0.103 1 0.024 4 0.062 3 0.065 2 0.063 8 C3 −0.000 4 −0.016 3 0.016 8 0.017 2 0.015 9 0.016 6 C4 −0.009 1 −0.022 9 0.013 6 0.022 7 0.013 8 0.018 2 C5 −0.061 5 −0.120 1 0.019 1 0.080 6 0.058 6 0.069 6 C6 −0.062 4 −0.125 5 −0.032 6 0.029 8 0.063 0 0.046 4 C9 −0.042 0 −0.105 0 0.018 2 0.060 2 0.063 0 0.061 6 C10 −0.046 1 −0.099 0 0.013 5 0.059 6 0.052 9 0.056 3 C13 −0.000 5 −0.029 3 0.061 4 0.061 9 0.028 7 0.045 3 C14 −0.044 3 −0.101 5 −0.010 1 0.034 1 0.057 2 0.045 7 C17 −0.046 1 −0.053 4 −0.035 5 0.010 6 0.007 3 0.008 9 O20 −0.249 7 −0.309 4 −0.206 6 0.043 1 0.059 7 0.051 4 C21 0.169 4 0.121 2 0.183 5 0.014 0 0.048 2 0.031 1 C25 −0.050 8 −0.061 2 −0.039 5 0.011 3 0.010 5 0.010 9 C28 0.004 0 −0.009 7 0.025 3 0.021 4 0.013 6 0.017 5 C32 −0.086 7 −0.104 1 −0.072 4 0.014 4 0.017 3 0.015 9 O33 −0.132 5 −0.151 0 −0.065 5 0.067 0 0.018 6 0.042 8
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表 4 UV/NH2Cl处理NMT主要降解产物质谱信息
Table 4. Mass spectra information of main degradation products for NM in UV/NH2Cl treatment
产物 保留时间/min [M-H]− 分子质量 分子式 NMT 7.03 227.107 4 228.110 6 C15H16O2 P1 7.30 259.096 8 260.100 1 C15H16O4 P2 5.18 258.111 3 259.114 7 C15H17NO3 P3 7.62 247.052 1 248.055 4 C14H13ClO2 P4 7.03 261.075 9 262.079 3 C14H14O5 P5 2.10 247.060 1 248.063 5 C13H12O5 P6 3.23 246.075 9 247.079 3 C13H13NO4 P7 5.76 265.026 8 266.030 0 C13H11ClO4 P8 6.92 290.066 3 291.069 6 C14H13NO6 P9 7.85 232.060 0 233.063 6 C12H11NO4
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