没食子酸加速卡马西平在Fe（Ⅲ）/PDS中的降解

doi:10.19965/j.cnki.iwt.2021-0242

摘要/Abstract

摘要：

Fe（Ⅱ）活化过二硫酸盐（PDS）产生的活性氧化剂能够降解卡马西平（CBZ）等难降解有机污染物，但Fe（Ⅲ）转化为Fe（Ⅱ）的速度较慢，限制了降解过程的效率。采用天然多酚化合物没食子酸（GA）强化Fe（Ⅲ）/PDS体系对CBZ的降解，同时研究降解效率、降解机理及转化路径。结果表明，反应25 min内CBZ降解率达到90.2%，降解速率常数为Fe（Ⅲ）/PDS体系的10倍。GA作为电子供体和还原剂有利于Fe（Ⅲ）的还原，可达到强化Fe（Ⅲ）活化PDS的效果。SO₄^·-和HO·为GA/Fe（Ⅲ）/PDS体系降解CBZ的主要活性氧物种。CBZ的降解率随GA、Fe（Ⅲ）和PDS浓度的增加而增加，但过量GA和PDS会猝灭活性自由基，降低CBZ的降解效率。初始pH由3.0提升至5.0可促进CBZ降解，而pH进一步增至7.0、9.0时Fe（Ⅲ）和Fe（Ⅱ）会转变为沉淀，导致PDS的活化效率降低。CBZ的降解途径主要为羟基化、羧化和氢原子提取。

关键词: 没食子酸, 卡马西平, 过硫酸盐, Fe（Ⅱ）循环

Abstract:

Fe(Ⅱ)-catalyzed persulfate(PDS) activation process is able to degrade refractory organic pollutants, such as carbamazepine(CBZ). However, the slow conversion rate of Fe(Ⅲ) to Fe(Ⅱ) restricted the efficiency of degradation process. Gallic acid(GA), a natural polyphenol compound, was employed to enhance the degradation of CBZ in the Fe(Ⅲ)/PDS system. Moreover, the degradation efficiency, mechanism and transformation pathway were studied. The results showed that the degradation rate of CBZ reached 90.2% within 25 minutes of the reaction, and the apparent rate constant was 10 times higher than that in the Fe(Ⅲ)/PDS system. As an electron donor and reducing agent, GA was beneficial to the reduction of Fe(Ⅲ) to strengthen Fe(Ⅲ) activation of PDS. SO₄^·- and HO· were the major reactive oxygen species for the degradation of CBZ in GA/Fe(Ⅲ)/PDS system. The degradation rate of CBZ increased with the increase of GA, Fe(Ⅲ) and PDS concentrations. However, excessive GA and PDS quenched the reactive radicals and reduced the degradation efficiency of CBZ. The increasing of initial pH from 3.0 to 5.0 promoted CBZ degradation. While the pH was further increased to 7.0 and 9.0, Fe(Ⅲ) and Fe(Ⅱ) were converted into precipitates, leading to a decrease in the activation efficiency of PDS. The degradation path of CBZ was mainly through hydroxylation, carboxylation and hydrogen atom extraction.

Key words: gallic acid, carbamazepine, persulfate, Fe(Ⅱ) recycle

中图分类号:

X703

杨应秋,魏杰. 没食子酸加速卡马西平在Fe（Ⅲ）/PDS中的降解[J]. 工业水处理, 2021, 41(12): 95-101.

Yingqiu YANG,Jie WEI. Degradation of carbamazepine in Fe(Ⅲ)/PDS system under gallic acid acceleration[J]. Industrial Water Treatment, 2021, 41(12): 95-101.

https://www.iwt.cn/CN/Y2021/V41/I12/95

图/表 7

图1 CBZ在不同反应体系中的降解情况

Fig.1 Degradation efficiency(a) and degradation kinetics(b) of CBZ in GA/Fe(Ⅲ)/PDS system

图2 铁离子浓度变化情况

Fig.2 Changes of Fe ion concentration in different system

图3 自由基清除剂对GA/Fe（Ⅲ）/PDS体系中CBZ降解的影响（a）；GA/Fe（Ⅲ）/PDS体系中EPR吸收波谱图（b）

Fig.3 Effect of radical scavengers on CBZ degradation in GA/Fe(Ⅲ)/PDS system(a); EPR absorption spectra of GA/Fe(Ⅲ)/PDS system(b)

图4 GA（a）、Fe（Ⅲ）（b）、PDS（c）对CBZ降解效果的影响

Fig.4 Effect of Ga(a), Fe(Ⅲ)(b), PDS(c) on the degradation of CBZ

图5 初始pH对GA/Fe（Ⅲ）/PDS体系降解CBZ的影响

Fig.5 Effect of initial pH on CBZ degradation in GA/Fe(Ⅲ)/PDS system

图6 CBZ在GA/Fe（Ⅲ）/PDS体系中的降解路径

Fig.6 Degradation pathway of CBZ in GA/Fe(Ⅲ)/PDS system

表1 ECOSAR模型评估的CBZ及转化产物对鱼类、水蚤、绿藻的急性和慢性毒性

Table 1 Acute and chronic toxicity of CBZ. and its transformation products to fish, Daphnia and green algae by ECOSAR model

项目	急性毒性/(mg_L^-1)		慢性毒性/(mg. L-¹)
项目	鱼类(96hLC₅₀)	水蚤(48hLC₅₀)	绿藻(96hEC₅₀)	鱼类(ChV)	水蚤(ChV)	绿藻ChV)
CBZ	40.9	14.1	0.260	1.05	1.17	0.096
TP270	1 910	4 630	2.57	87.2	99.8	0.888
TP264	46.7	18.8	4.09	4.55	2.00	8.34
TP252A	86.5	28.8	7.45	8.08	2.85	13.8
TP252B	234	116	0.605	5.27	5.91	0.218
TP250	39.0	16.3	3.42	3.83	1.75	7.12
TP239	11.8	10.6	6.35	1.56	0.123	2.56
TP223	153	97.3	115	17.1	12.9	38.4
TP209	4.15	3.42	2.26	0.352	0.047	1.05
TP195	308	170	112	29.1	15.3	27.5
TP179	9.63	6.18	7.61	1.09	0.845	2.61

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