真空紫外/亚硫酸盐体系降解抗病毒药物的效能与机制

doi:10.19965/j.cnki.iwt.2024-0487

摘要/Abstract

摘要：

利巴韦林（RBV）作为典型抗病毒药物，使用量激增，现有污水处理工艺对其去除效能极为有限，导致其向外界水环境释放，引起水生态安全隐患。考察了真空紫外（VUV）/亚硫酸盐体系对RBV的降解效能与机制。结果表明，VUV/亚硫酸盐体系可以高效降解RBV。当亚硫酸盐投加量为10 mmol/L，溶液pH=9，紫外光辐照度为4 800 μW/cm²时，初始浓度为41.0 μmol/L的RBV经VUV/亚硫酸盐体系反应180 min，降解率超过95%，RBV降解的表观速率常数为0.013 5 min^-1。相较于单独VUV体系，VUV/亚硫酸盐体系中RBV降解率的提升主要由强还原物种水合电子（e_aq ^-）增加引起。RBV降解速率随紫外光辐照度和溶液pH的升高而加快，随RBV初始浓度的增加而减慢。共存离子Br^-、HCO₃ ^-和有机物HA均会抑制VUV/亚硫酸盐体系对RBV的降解。RBV在VUV/亚硫酸盐体系中存在3条降解路径，主要涉及酰胺键的断裂、羧基的形成及脱羧、呋喃核糖上羟甲基的氧化、醚键和碳氮键的断裂。

关键词: 利巴韦林, 抗病毒药物, 真空紫外, 亚硫酸盐, 水合电子

Abstract:

The extensive use of ribavirin (RBV) as a typical antiviral drug has led to its substantial release into aquatic environments due to the limited removal efficiency of the existing wastewater treatment processes, posing potential ecological safety risks. This study investigated the efficiency and mechanism of RBV degradation by the VUV/sulfite system. The results showed that RBV could be efficiently degraded by the VUV/sulfite system. The degradation rate of RBV (initial concentration of 41.0 μmol/L) reached over 95% after 180 min reaction at sulfite dosage of 10 mmol/L, solution pH of 9 and UV irradiance of 4 800 μW/cm²,with an observed rate constant of 0.013 5 min^-1. Compared with VUV, the enhancement of RBV degradation in the investigated system was attributed to the increase of hydrated electron (e_aq ^-), which was a highly reductive species. RBV degradation rate was accelerated with the increase of UV intensity and solution pH, but slowed with the increase of initial RBV concentration. The co-existing ions (i.e. Br^-, HCO₃ ^-) and organic substances (humic acid) all inhibited RBV removal by the VUV/sulfite system. There were three degradation pathways of RBV by the VUV/sulfite system, which mainly involved the break of amide group, the formation of carboxy and decarboxylation, the oxidation of hydroxymethy group connected to the ribofuranose, the break of ether bond and carbon nitrogen bond.

Key words: ribavirin, antiviral drug, vacuum ultraviolet, sulfite, hydrated electron

中图分类号:

X703

顾玉蓉, 阚晓东, 董紫君, 张毅, 韩琦. 真空紫外/亚硫酸盐体系降解抗病毒药物的效能与机制[J]. 工业水处理, 2025, 45(7): 73-80.

Yurong GU, Xiaodong KAN, Zijun DONG, Yi ZHANG, Qi HAN. Efficiency and mechanism of degradation of an antiviral drug by VUV/sulfite system[J]. Industrial Water Treatment, 2025, 45(7): 73-80.

https://www.iwt.cn/CN/Y2025/V45/I7/73

图/表 12

参考文献 37

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影响因素	参数设置	其他反应条件
溶液pH	4、6、7、9、10	［RBV］₀=41.0 μmol/L、［SO₃ ^2-］₀=10 mmol/L、辐照度I ₀
RBV初始浓度	20.5、41.0、61.4 μmol/L	［SO₃ ^2-］₀=10 mmol/L、pH=9、辐照度I ₀
亚硫酸盐浓度	5、10、15 mmol/L	［RBV］₀=41.0 μmol/L、pH=9、辐照度I ₀
光强	I ₀/3、I ₀	［RBV］₀=41.0 μmol/L、［SO₃ ^2-］₀=10 mmol/L、pH=9
共存物质	［HCO₃ ^-］=2 mmol/L、［Cl^-］=2 mmol/L、［Br^-］=2 mmol/L、［HA］=5 mg/L	［RBV］₀=41.0 μmol/L、［SO₃ ^2-］₀=10 mmol/L、pH=9、辐照度I ₀

影响因素	参数设置	其他反应条件
溶液pH	4、6、7、9、10	［RBV］₀=41.0 μmol/L、［SO₃ ^2-］₀=10 mmol/L、辐照度I ₀
RBV初始浓度	20.5、41.0、61.4 μmol/L	［SO₃ ^2-］₀=10 mmol/L、pH=9、辐照度I ₀
亚硫酸盐浓度	5、10、15 mmol/L	［RBV］₀=41.0 μmol/L、pH=9、辐照度I ₀
光强	I ₀/3、I ₀	［RBV］₀=41.0 μmol/L、［SO₃ ^2-］₀=10 mmol/L、pH=9
共存物质	［HCO₃ ^-］=2 mmol/L、［Cl^-］=2 mmol/L、［Br^-］=2 mmol/L、［HA］=5 mg/L	［RBV］₀=41.0 μmol/L、［SO₃ ^2-］₀=10 mmol/L、pH=9、辐照度I ₀

降解方法	反应条件	RBV降解率/%	反应时间/h	K _obs/min^-1	参考文献
Fe（Ⅵ）+乙酰丙酮（AA）	［Fe（Ⅵ）］₀=1.660 mmol/L、［AA］₀=0.415 mmol/L、［RBV］₀=41.5 μmol/L、pH=9	≈80	2	0.996	〔21〕
Fe（Ⅵ）	［Fe（Ⅵ）］₀=83 μmol/L、［RBV］₀=41.5 μmol/L、pH=8	14.2	2		〔22〕
O₃/PMS	［O₃］₀=0.025 mmol/L、［PMS］₀=0.025 mmol/L、［RBV］₀=10 μmol/L、pH=7	≈50	0.25	25.92	〔23〕
Cl₂	［RBV］₀=5 mg/L、［自由氯］=5 mg/L	>97	24		〔24〕
UV/NaClO/TEMPO	［RBV］₀=10 mg/L、［自由氯］=42 μmol/L、［TEMPO］₀=0.1 μmol/L、pH=7	≈15	1/6	0.015 4	〔25〕
UV/H₂O₂	［H₂O₂］₀=200 μmol/L、［RBV］₀=1 μmol/L、pH=7	≈80	1.5		〔26〕
UV/TiO₂	［RBV］₀=1 μmol/L、［TiO₂］₀=200 μmol/L	≈60	1/3		〔27〕
VUV/亚硫酸盐	［Na₂SO₃］₀=10 mmol/L、［RBV］₀=41.0 μmol/L	96.2	3	0.013 5	本研究

降解方法	反应条件	RBV降解率/%	反应时间/h	K _obs/min^-1	参考文献
Fe（Ⅵ）+乙酰丙酮（AA）	［Fe（Ⅵ）］₀=1.660 mmol/L、［AA］₀=0.415 mmol/L、［RBV］₀=41.5 μmol/L、pH=9	≈80	2	0.996	〔21〕
Fe（Ⅵ）	［Fe（Ⅵ）］₀=83 μmol/L、［RBV］₀=41.5 μmol/L、pH=8	14.2	2		〔22〕
O₃/PMS	［O₃］₀=0.025 mmol/L、［PMS］₀=0.025 mmol/L、［RBV］₀=10 μmol/L、pH=7	≈50	0.25	25.92	〔23〕
Cl₂	［RBV］₀=5 mg/L、［自由氯］=5 mg/L	>97	24		〔24〕
UV/NaClO/TEMPO	［RBV］₀=10 mg/L、［自由氯］=42 μmol/L、［TEMPO］₀=0.1 μmol/L、pH=7	≈15	1/6	0.015 4	〔25〕
UV/H₂O₂	［H₂O₂］₀=200 μmol/L、［RBV］₀=1 μmol/L、pH=7	≈80	1.5		〔26〕
UV/TiO₂	［RBV］₀=1 μmol/L、［TiO₂］₀=200 μmol/L	≈60	1/3		〔27〕
VUV/亚硫酸盐	［Na₂SO₃］₀=10 mmol/L、［RBV］₀=41.0 μmol/L	96.2	3	0.013 5	本研究

体系	C/C ₀	V/L	t/min	P/kW	亚硫酸盐消耗量/（mmol·L^-1）	EE/O_VUV/（kW·h·m^-3）	EE/O_亚硫酸盐/（kW·h·m^-3）	EE/O_总/（kW·h·m^-3）
VUV/亚硫酸盐	0.1	3	180	0.01	10	10	7.455	17.455
VUV	0.1	3	240	0.01	0	13.333	0	13.333

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