Degradation of Climbazole by Ozonation: Influencing Factors and Degradation Products
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摘要: 唑类抗真菌剂广泛应用于药物和个人护理品(pharmaceutical and personal care products，PPCPs)中，常规污水处理工艺难以将其有效去除. 大量唑类抗真菌剂排入受纳环境后会对生态系统造成一系列负面影响. 为了解唑类抗真菌剂的臭氧氧化降解过程和机理，以氯咪巴唑(climbazole，CZ)为例，通过设置不同条件的对比试验，系统研究CZ在臭氧氧化过程中的影响因素及其去除规律，同时采用超高效液相色谱-飞行时间质谱联用仪UPLC-Q/TOF对其降解产物进行鉴定. 影响因素试验结果表明：①CZ起始浓度由1.0 mg/L增至4.0 mg/L时，臭氧氧化20 min下CZ的降解率从99.1%降至69.3%；②反应体系起始pH由5.0升至9.0时，CZ臭氧降解半衰期由1.38 min延长至7.18 min；③臭氧流速由0.1 L/min增至0.4 L/min时，臭氧氧化20 min时CZ的降解率从66.5%提至99.4%，但臭氧流速超过0.3 L/min以后，CZ降解率的增幅较小；④自然水体及其高浓度共存组分(碳酸氢根和腐殖酸)均会明显抑制CZ的臭氧氧化反应速率，CZ降解半衰期大多数超过6 min (空白对照组为1.99 min). 因此，在臭氧氧化降解新兴有机污染物或对臭氧氧化工艺进行优化时，应充分考虑起始污染负荷、pH、臭氧流速、水体水质状况等对处理效果的影响. 产物鉴定结果表明：臭氧氧化反应可将CZ碎裂重组形成两个主要降解产物——TP269和TP297，二者的产率分别为11.45%和8.90%. 研究显示，起始污染负荷、pH、臭氧流速、水体水质状况均会明显影响CZ的臭氧降解效果；两个CZ臭氧降解产物的产率虽不高，但其毒性有待进一步研究.Abstract: Azole antifungals are widely used in pharmaceutical and personal care products (PPCPs), and they are difficult to be removed by conventional wastewater treatment processes. A large amount of azole antifungals discharged into the receiving environment may cause a series of negative effects. In order to understand the degradation kinetics and mechanism of azole antifungals by ozonation, climbazole (CZ) was selected as the target compound, the influencing factors and removal law were systematically studied through setting comparative experiments under different ozonation conditions, and the degradation products were identified by UPLC-Q/TOF. The results showed that: (1) When the initial CZ concentration increased from 1.0 mg/L to 4.0 mg/L, the degradation of CZ at 20 min ozonation decreased from 99.1% to 69.3%. (2) The half-lives of CZ degradation by ozone increased from 1.38 min to 7.18 min with the increase of the initial pH from 5.0 to 9.0. (3) The degradation of CZ at 20 min ozonation increased from 66.5% to 99.4% when the ozone flow rate increased from 0.1 L/min to 0.4 L/min, but it increased very slow when the ozone flow rate exceeded 0.3 L/min. (4) Natural water and its coexisting components (high concentration of bicarbonate radical and humic acid) showed significant inhibition effects on the degradation of CZ in ozonation process, where the degradation half-lives of CZ were more than 6 min (1.99 min for blank controller) in most cases. Therefore, the influence factors such as initial pollution load, pH value, ozone flow rate and water quality should be considered when using ozonation as a treatment technology to remove emerging organic pollutants. Two main CZ degradation products (TP269 and TP297) were formed through fracturing and restructuring in the ozonation treatment, with the products yields of 11.45% and 8.90%, respectively. Above results reveals that ozone degradation effect of CZ can be influence obviously by initial pollution load, pH value, ozone flow rate and water quality etc. The yields of two CZ degradation products were very low, but their toxicity needs to be studied.
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Key words:
- ozonation /
- climbazole /
- influencing factors /
- degradation rate /
- half-life /
- degradation products
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图 2 起始CZ浓度对臭氧氧化降解CZ的影响
Figure 2. Effects of initial CZ concentrations on the ozonation degradation of CZ
图 3 溶液起始pH对臭氧氧化降解CZ的影响
Figure 3. Effects of initial pH of solution on the ozonation degradation of CZ
图 4 臭氧流速对臭氧氧化降解CZ的影响
Figure 4. Effects of ozone flow rates on the ozonation degradation of CZ
图 5 碳酸氢根浓度对臭氧氧化降解CZ的影响
Figure 5. Effects of bicarbonate radical concentrations on the ozonation degradation of CZ
图 6 腐殖酸浓度对臭氧氧化降解CZ的影响
Figure 6. Effects of humic acid concentrations on the ozonation degradation of CZ
图 7 自然水体对臭氧氧化降解CZ的影响
Figure 7. Effects of natural waters on the ozonation degradation of CZ
图 8 CZ臭氧氧化样品进行UPLC-Q/TOF (ESI+)全扫描总离子流图
Figure 8. The chromatogram of the ozonation reaction solution of CZ analyzed by UPLC-Q/TOF(ESI+)
图 9 高能通道下CZ臭氧降解产物TP269的MSE离子碎片匹配结果
Figure 9. MSE ionic fragment matching diagram for the ozonation degradation products TP269 of CZ under the high-energy channel
图 10 臭氧氧化反应全过程CZ母体及其产物的浓度变化
Figure 10. Concentration changes of CZ and its products in the whole process of ozonation
表 1 臭氧氧化降解CZ的试验条件设置
Table 1. Experimental condition setting for the ozonation degradation of CZ
影响
因素起始CZ浓度/
(mg/L)起始pH 臭氧流速/
(L/min)碳酸氢钠添加浓度/
(mg/L)腐殖酸添加浓度/
(mg/L)自然水体类型 起始CZ浓度 1.0、2.0、3.0、4.0 7.0 0.2 0 0 纯水 起始pH 3.0 5.0、7.0、 9.0 0.2 0 0 纯水 臭氧流速 3.0 7.0 0.1、0.2、0.3、0.4 0 0 纯水 碳酸氢根浓度 3.0 7.0 0.2 0、10、20、50、100 0 纯水 腐殖酸浓度 3.0 7.0 0.2 0 0、1.0、3.0、6.0、9.0 纯水 自然水体类型 3.0 7.0 0.2 0 0 纯水、珠江河水、水厂二级进水、自来水 
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表 2 氯咪巴唑及其臭氧降解产物质谱测定信息汇总
Table 2. Information summary of mass spectrometry measurement for climbazole and its ozonation transformation products (TPs)
母体/产物 保留时
间/min准确质
量数加和离子
(+H或+Na)仪器测定的
质荷比(m/z)分子式 不饱和
度/Ω质量数
偏差/10−6匹配分析
置信度(i-FIT
confidence)/%MS/MS碎
片(m/z)氯咪巴唑(climbazole) 7.71 292.097 9 +H 293.104 20 C15H17ClN2O2 8 — — 197.071 90、129.008 32 TP269 8.41 269.081 9 +Na 292.071 76 C13H16ClNO3 6 -2.5 99.85 196.018 09、168.022 88、
164.069 45、141.011 21、
140.026 95、TP297 9.79 297.076 8 +Na 320.066 42 C14H16ClNO4 7 -2.6 97.42 320.066 42
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