等离子体射流耦合活性碳纤维去除水中糖皮质激素

doi:10.16085/j.issn.1000-6613.2021-0913

摘要/Abstract

摘要：

糖皮质激素（glucocorticoids，GCs）作为一类环境内分泌干扰物，引起了环境领域越来越多的关注。由于缺乏有效控制水中GCs污染的技术，本研究搭建了并联等离子体射流耦合活性碳纤维系统（paralleling plasma jet/activated carbon fiber，PPJ/ACF）以有效降解水中的糖皮质激素氟轻松（fluocinolone acetonide，FA）。当PPJ/ACF系统的放电功率为49.7W、ACF投加量为3g/L时，处理60min后，FA的去除率可达96 %，能量利用率为96mg/kWh，能耗量为0.36kWh/L。PPJ与ACF联用有显著的协同效应，ACF可提供催化位点及吸附GCs位点，PPJ可原位释放ACF吸附位点。通过添加自由基抑制剂，发现羟基自由基（·OH）是降解FA的主要作用自由基。通过超高效液相色谱飞行时间质谱联用仪（ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometer，UHPLC-QTOF）检测分析了FA可能的中间产物，根据中间产物分析FA的降解途径主要包括脱氟、酮酸脱羧、脱甲基、分子内环化、裂解和酯水解，表明FA毒性降低。因此，PPJ/ACF系统可有效控制GCs污染。

关键词: 糖皮质激素, 等离子体射流, 活性碳纤维, 氟轻松, 降解机理

Abstract:

Glucocorticoids (GCs), as a kind of environmental endocrine disruptors, have attracted increasing attention in the field of environment. Due to the lack of technology to effectively control GC pollution in water, this research built a paralleling plasma jet/activated carbon fiber (PPJ/ACF) system to effectively degrade fluocinolone acetonide (FA). At PPJ discharge power of 49.7W and ACF dosage of 3g/L, the removal efficiency of FA reached 96% at 60min with energy yield of 96mg/kWh and energy consumption of 0.36kWh/L. The combination of PPJ and ACF showed significant synergistic effects. During PPJ treatment, the added ACF provided catalytic sites and adsorption sites for GCs. In the meantime, PPJ released ACF adsorption sites in situ. In PPJ/ACF system, hydroxyl radicals (·OH) were identified as the functional reactive species for FA degradation by radical scavengers. Transformation intermediates with lower lipophilicity and toxicity were identified by ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometer (UHPLC-QTOF), indicating possible degradation pathways of FA including defluorination, keto acid decarboxylation, demethylation, intramolecular cyclization, cleavage and esterolysis. Overall, this study provides an effective and practical way to control GC pollution by PPJ/ACF treatment.

Key words: glucocorticoids, paralleling plasma jet, activated carbon fiber, synergistic effects, degradation mechanisms

中图分类号:

X592

周永泉, 张艾, 刘亚男, 王铮. 等离子体射流耦合活性碳纤维去除水中糖皮质激素[J]. 化工进展, 2022, 41(4): 2209-2215.

ZHOU Yongquan, ZHANG Ai, LIU Yanan, WANG Zheng. Removal of glucocorticoids from aqueous solution by plasma jet combined with activated carbon fiber[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 2209-2215.

图/表 10

图1 实验装置（石英鼓泡反应器）示意图

图2 联用ACF对PPJ降解FA的影响（放电功率为34.8W，ACF投加量为1g/L）

图3 放电功率对PPJ/ACF联用去除FA的效果及能量利用率的影响（处理时间为60min，ACF投加量为1g/L）

图4 ACF投加量对PPJ/ACF联用去除FA的效果及能量利用率的影响（放电功率为49.7W，反应时间为60min）

图5 ACF的SEM图

表1 ACF和PPJ-ACF的BET测试数据

被测样品	比表面积/m2·g^-1	单点吸附总孔/cm3·g^-1
处理前的ACF	1516.41	0.62
PPJ处理后的ACF	1669.76	0.68

图6 自由基抑制剂对FA去除的影响（处理时间为60min，放电功率为49.7W，ACF投加量为3g/L）TBA—100mmol/L，捕获·OH；BQ—100mmol/L，捕获·O2-；DABCO—100mmol/L，捕获1O2

图7 PPJ/ACF技术在降解FA的综合机制示意图

表2 PPJ/ACF降解FA的中间产物信息

产物	m/z	分子式	相对分子量	误差
FA-P₄₈₆	485.1987	C₂₄H₃₂F₂O₈	486.2065	1.19 $×$ 10^-6
FA-P₄₂₈	427.1778	C₂₄H₂₈O₇	428.1835	-2.67 $×$ 10^-6
FA-P₃₂₈	327.1414	C₂₀H₂₁FO₃	328.1475	-2.97 $×$ 10^-6
FA-P₃₅₀	349.1457	C₁₉H₂₃FO₅	350.1530	-0.15 $×$ 10^-6
FA-P₃₉₀	389.1406	C₁₈H₂₄F₂O₇	390.1490	2.83 $×$ 10^-6
FA-P₃₃₂	331.1367	C₁₆H₂₂F₂O₅	332.1435	1.21 $×$ 10^-6

表2 PPJ/ACF降解FA的中间产物信息

产物	m/z	分子式	相对分子量	误差
FA-P₄₈₆	485.1987	C₂₄H₃₂F₂O₈	486.2065	1.19 $×$ 10^-6
FA-P₄₂₈	427.1778	C₂₄H₂₈O₇	428.1835	-2.67 $×$ 10^-6
FA-P₃₂₈	327.1414	C₂₀H₂₁FO₃	328.1475	-2.97 $×$ 10^-6
FA-P₃₅₀	349.1457	C₁₉H₂₃FO₅	350.1530	-0.15 $×$ 10^-6
FA-P₃₉₀	389.1406	C₁₈H₂₄F₂O₇	390.1490	2.83 $×$ 10^-6
FA-P₃₃₂	331.1367	C₁₆H₂₂F₂O₅	332.1435	1.21 $×$ 10^-6

图8 FA在PPJ/ACF处理过程中的中间产物分析

参考文献 20

21	CLENNAN E L, PACE A. Advances in singlet oxygen chemistry[J]. Tetrahedron, 2005, 61(28): 6665-6691.
22	JOSHI A A, LOCKE B R, ARCE P, et al. Formation of hydroxyl radicals, hydrogen peroxide and aqueous electrons by pulsed streamer corona discharge in aqueous solution[J]. Journal of Hazardous Materials, 1995, 41(1): 3-30.
23	PAN Y H, CHENG S S, YANG X, et al. UV/chlorine treatment of carbamazepine: transformation products and their formation kinetics[J]. Water Research, 2017, 116: 254-265.
24	IQBAL J, GUPTA A, HUSAIN A. Photochemistry of clobetasol propionate, a steroidal anti-inflammatory drug[J]. ARKIVOC, 2006(11): 91-98.
25	LIAN L, YAN S, YAO B, et al. Photochemical transformation of nicotine in wastewater effluent[J]. Environmental Science & Technology, 2017, 51(20): 11718-11730.
26	LI Y Y, PAN Y H, LIAN L S, et al. Photosensitized degradation of acetaminophen in natural organic matter solutions: the role of triplet states and oxygen[J]. Water Research, 2017, 109: 266-273.
27	RAZAVI B, SONG W H, SANTOKE H, et al. Treatment of statin compounds by advanced oxidation processes: kinetic considerations and destruction mechanisms[J]. Radiation Physics and Chemistry, 2011, 80(3): 453-461.
1	SEGAL S K, SIMON R, MCFARLIN S, et al. Glucocorticoids interact with noradrenergic activation at encoding to enhance long-term memory for emotional material in women[J]. Neuroscience, 2014, 277: 267-272.
2	中华人民共和国国家卫生健康委员会. 新型冠状病毒感染的肺炎诊疗方案（试行第七版）（国卫办医函[2020]184号）[EB/OL]. (2020-03-03). .
	National Health Commission of the People's Republic of China. Scheme for Diagnosis and Treatment of 2019 Novel Coronavirus Pneumonia (The 7th Trial Edition)[EB/OL].[2020-03-03]. .
3	SHARGIL D, FINE P, GERSTL Z, et al. Impact of biosolids and wastewater effluent application to agricultural land on corticosterone content in lettuce plants[J]. Science of the Total Environment, 2016, 541: 742-749.
4	HIDASI A O, GROH K J, SUTER M J F, et al. Clobetasol propionate causes immunosuppression in zebrafish (Danio rerio) at environmentally relevant concentrations[J]. Ecotoxicology and Environmental Safety, 2017, 138: 16-24.
5	LALONE C A, VILLENEUVE D L, OLMSTEAD A W, et al. Effects of a glucocorticoid receptor agonist, dexamethasone, on fathead minnow reproduction, growth, and development[J]. Environmental Toxicology and Chemistry, 2012, 31(3): 611-622.
6	SANDS J, CREEL S. Social dominance, aggression and faecal glucocorticoid levels in a wild population of wolves, Canis lupus[J]. Animal Behaviour, 2004, 67(3): 387-396.
7	ROBERTS J, BAIN P A, KUMAR A, et al. Tracking multiple modes of endocrine activity in Australia's largest inland sewage treatment plant and effluent-receiving environment using a panel of in vitro bioassays[J]. Environmental Toxicology and Chemistry, 2015, 34(10): 2271-2281.
8	DONG X Y, YUAN X, WANG R J. Interaction of air cold plasma with Saccharomyces cerevisiae in the multi-scale microenvironment for improved ethanol yield[J]. Bioresource Technology, 2021, 323: 124621.
9	DONG X Y, YANG Y L. A novel approach to enhance blueberry quality during storage using cold plasma at atmospheric air pressure[J]. Food and Bioprocess Technology, 2019, 12(8): 1409-1421.
10	LIU Y N, WANG C H, SHEN X, et al. Degradation of glucocorticoids in aqueous solution by dielectric barrier discharge: kinetics, mechanisms, and degradation pathways[J]. Chemical Engineering Journal, 2019, 374: 412-428.
11	LI K L, NING P, LI K, et al. Low temperature catalytic hydrolysis of carbon disulfide on activated carbon fibers modified by non-thermal plasma[J]. Plasma Chemistry and Plasma Processing, 2017, 37(4): 1175-1191.
12	AJO P, PREIS S, VORNAMO T, et al. Hospital wastewater treatment with pilot-scale pulsed corona discharge for removal of pharmaceutical residues[J]. Journal of Environmental Chemical Engineering, 2018, 6(2): 1569-1577.
13	JIA A, WU S, DANIELS K D, et al. Balancing the budget: accounting for glucocorticoid bioactivity and fate during water treatment[J]. Environmental Science & Technology, 2016, 50(6): 2870-2880.
14	SUN Y, LIU Y N, LI R, et al. Degradation of reactive blue 19 by needle-plate non-thermal plasma in different gas atmospheres: kinetics and responsible active species study assisted by CFD calculations[J]. Chemosphere, 2016, 155: 243-249.
15	LI S P, MA X L, JIANG Y Y, et al. Acetamiprid removal in wastewater by the low-temperature plasma using dielectric barrier discharge[J]. Ecotoxicology and Environmental Safety, 2014, 106: 146-153.
16	XIN L, SUN Y B, FENG J W, et al. Degradation of triclosan in aqueous solution by dielectric barrier discharge plasma combined with activated carbon fibers[J]. Chemosphere, 2016, 144: 855-863.
17	KIM K S, YANG C S, MOK Y S. Degradation of veterinary antibiotics by dielectric barrier discharge plasma[J]. Chemical Engineering Journal, 2013, 219: 19-27.
18	PEGO M F F, BIANCHI M L, CARVALHO J A, et al. Surface modification of activated carbon by corona treatment[J]. Anais Da Academia Brasileira De Ciências, 2019, 91(1): e20170947.
19	JIANG B, ZHENG J T, LIU Q, et al. Degradation of azo dye using non-thermal plasma advanced oxidation process in a circulatory airtight reactor system[J]. Chemical Engineering Journal, 2012, 204/205/206: 32-39.
20	ZHANG Yanzong, ZHENG Jingtang, QU Xianfeng, et al. Catalytic effect of activated carbon and activated carbon fiber in non-equilibrium plasma-based water treatment[J]. Plasma Science and Technology, 2008, 10(3): 358-362.

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