类固醇雌激素在水环境中的分布及其深度去除技术研究进展

doi:10.11894/iwt.2020-1266

摘要/Abstract

摘要：

类固醇雌激素（SEs）是水环境中高频检出的一类微量难降解有机物，其在我国大部分水体中的残留质量浓度往往超过欧盟规定的雌激素干扰效应质量浓度阈值1 ng/L，对生态环境及人体产生潜在健康风险，是影响二级生化尾水深度处理后安全再利用的重要污染物。综述了类固醇雌激素的理化性质、在水环境中的分布特征及其潜在环境风险，并对其主要的深度去除技术进行了总结。在此基础上，从新型吸附材料、经济高效的催化氧化技术、多污染物协同深度净化、组合工艺及反应器开发等四个方面展望了未来的研究趋势。

关键词: 类固醇雌激素, 水环境风险, 污水深度处理, 再生水安全利用

Abstract:

Steroid estrogens(SEs) are a group of refractory organic micropollutants detected in aquatic environment frequently. Generally, their mass concentrations in aquatic environment of China are much higher than estrogen disruption effects mass concentration threshold of 1 ng/L, which results in potential health risks to the environment and human. They are vital pollutants affecting the safe reuse of secondary effluent after the advanced treatment. This study systematically reviewed that the physical and chemical properties, the distribution in aquatic environment and the potential environment risks of steroid estrogens. The main advanced removal techniques for steroid estrogens were also summarized. On this basis, the future research trends were proposed from four aspects including new adsorption materials, inexpensive catalytic oxidation technology, synergistic advance purification of multi-pollutants, development of combined process and reactors.

Key words: steroid estrogen, aquatic environment risk, advanced wastewater treatment, safe reuse of reclaimed water

中图分类号:

X703

胡俊,李同,颜宇杰,黄辉,张徐祥,任洪强. 类固醇雌激素在水环境中的分布及其深度去除技术研究进展[J]. 工业水处理, 2021, 41(6): 58-65.

Jun Hu,Tong Li,Yujie Yan,Hui Huang,Xuxiang Zhang,Hongqiang Ren. Distribution of steroid estrogen in aquatic environment and research progress of their advanced removal technologies[J]. Industrial Water Treatment, 2021, 41(6): 58-65.

https://www.iwt.cn/CN/Y2021/V41/I6/58

图/表 5

参考文献 54

1	崔琦, 陈卓, 李魁晓, 等. 再生水系统的可靠性: 内涵及其保障措施[J]. 环境工程, 2019, 37 (12): 75- 79. URL
2	阳春, 胡碧波, 张智. 类固醇雌激素在生活污水处理中的去除过程[J]. 中国给水排水, 2008, 24 (10): 11- 15. doi: 10.3321/j.issn:1000-4602.2008.10.003
3	Ekpeghere K I , Sim W J , Lee H J , et al. Occurrence and distribution of carbamazepine, nicotine, estrogenic compounds, and their transformation products in wastewater from various treatment plants and the aquatic environment[J]. Science of the Total Environment, 2018, 640/641, 1015- 1023. doi: 10.1016/j.scitotenv.2018.05.218
4	Ma Mei , Rao Kaifeng , Wang Zijian . Occurrence of estrogenic effects in sewage and industrial wastewaters in Beijing, China[J]. Environmental Pollution, 2007, 147 (2): 331- 336. doi: 10.1016/j.envpol.2006.05.032
5	余薇薇, 朱家悦, 陈垚, 等. 集约化养殖场中类固醇雌激素的环境行为与处理途径[J]. 环境工程, 2017, 35 (3): 174- 178. URL
6	林建德, 邵坚, 冯成洪, 等. 天然类固醇雌激素源解析、环境行为及其污染控制[J]. 环境科学与技术, 2012, 35 (5): 60- 64. doi: 10.3969/j.issn.1003-6504.2012.05.014
7	都韶婷, 金崇伟, 刘越. 水体类固醇雌激素污染现状研究进展[J]. 环境科学, 2013, 34 (9): 3358- 3367. URL
8	Su Chao , Cui Yan , Liu Di , et al. Endocrine disrupting compounds, pharmaceuticals and personal care products in the aquatic environment of China: Which chemicals are the prioritized ones?[J]. Science of the Total Environment, 2020, 720, 137652. doi: 10.1016/j.scitotenv.2020.137652
9	Tan Ruijie , Liu Ruixia , Li Bin , et al. Typical endocrine disrupting compounds in rivers of northeast China: Occurrence, partitioning, and risk assessment[J]. Archives of Environmental Contamination and Toxicology, 2018, 75 (2): 213- 223. doi: 10.1007/s00244-017-0482-x
10	Wang Wenfeng , Ndungu A W , Wang Jun . Monitoring of endocrinedisrupting compounds in surface water and sediments of the Three Gorges Reservoir Region, China[J]. Archives of Environmental Contamination and Toxicology, 2016, 71 (4): 509- 517. doi: 10.1007/s00244-016-0319-z
11	Luo Zhoufei , Tu Yi , Li Haipu , et al. Endocrine-disrupting compounds in the Xiangjiang River of China: Spatio-temporal distribution, source apportionment, and risk assessment[J]. Ecotoxicology and Environmental Safety, 2019, 167, 476- 484. doi: 10.1016/j.ecoenv.2018.10.053
12	Yang Yuyi , Cao Xinhua , Zhang Miaomiao , et al. Occurrence and distribution of endocrine-disrupting compounds in the Honghu Lake and East Dongting Lake along the Central Yangtze River, China[J]. Environmental Science and Pollution Research, 2015, 22 (22): 17644- 17652. doi: 10.1007/s11356-015-4980-y
13	Lv Jian , Zhang Cui , Wu Jun , et al. Seasonal distribution, risks, and sources of endocrine disrupting chemicals in coastal waters: Will these emerging contaminants pose potential risks in marine environment at continental-scale?[J]. Chemosphere, 2020, 247, 125907. doi: 10.1016/j.chemosphere.2020.125907
14	Wang Song , Zhu Zeliang , He Jiafa , et al. Steroidal and phenolic endocrine disrupting chemicals(EDCs) in surface water of Bahe River, China: Distribution, bioaccumulation, risk assessment and estrogenic effect on Hemiculter leucisculus[J]. Environmental Pollution, 2018, 243, 103- 114. doi: 10.1016/j.envpol.2018.08.063
15	Huang Bin , Xiong Dan , He Huan , et al. Characteristics and bioaccumulation of progestogens, androgens, estrogens, and phenols in Erhai Lake Catchment, Yunnan, China[J]. Environmental Engineering Science, 2017, 34 (5): 321- 332. doi: 10.1089/ees.2016.0118
16	Huang Bin , Wang Bin , Ren Dong , et al. Occurrence, removal and bioaccumulation of steroid estrogens in Dianchi Lake catchment, China[J]. Environment International, 2013, 59, 262- 273. doi: 10.1016/j.envint.2013.06.018
17	Lei Bingli , Huang Shengbiao , Zhou Yiqi , et al. Levels of six estrogens in water and sediment from three rivers in Tianjin area, China[J]. Chemosphere, 2009, 76 (1): 36- 42. doi: 10.1016/j.chemosphere.2009.02.035
18	Combalbert S , Hernandez-Raquet G . Occurrence, fate, and biodegradation of estrogens in sewage and manure[J]. Applied Microbiology and Biotechnology, 2010, 86 (6): 1671- 1692. doi: 10.1007/s00253-010-2547-x
19	Glineur A , Nott K , Carbonnelle P , et al. Development and validation of a method for determining estrogenic compounds in surface water at the ultra-trace level required by the Eu water framework directive watch list[J]. Journal of Chromatography A, 2020, 1624, 461242. doi: 10.1016/j.chroma.2020.461242
20	Lei Kai , Lin Chunye , Zhu Ying , et al. Estrogens in municipal wastewater and receiving waters in the Beijing-Tianjin-Hebei region, China: Occurrence and risk assessment of mixtures[J]. Journal of Hazardous Materials, 2020, 389, 121891. doi: 10.1016/j.jhazmat.2019.121891
21	Johnson A C , Belfroid A , Di Corcia A . Estimating steroid oestrogen inputs into activated sludge treatment works and observations on their removal from the effluent[J]. Science of the Total Environment, 2000, 256 (2): 163- 173. URL
22	Fawell J K , Sheahan D A , James H A , et al. Oestrogens and oestrogenic activity in raw and treated water in Severn Trent Water[J]. Water Research, 2001, 35 (5): 1240- 1244. doi: 10.1016/S0043-1354(00)00367-5
23	Petrovic M , Sole M , De Alda M J L , et al. Endocrine disruptors in sewage treatment plants, receiving river waters, and sediments: Integration of chemical analysis and biological effects on feral carp[J]. Environmental Toxicology and Chemistry, 2002, 21 (10): 2146- 2156. doi: 10.1002/etc.5620211018
24	Cargouet M , Perdiz D , Mouatassimsouali A , et al. Assessment of river contamination by estrogenic compounds in Paris area(France)[J]. Science of the Total Environment, 2004, 324 (1): 55- 66. URL
25	Ekpeghere K I , Sim W J , Lee H J , et al. Occurrence and distribution of carbamazepine, nicotine, estrogenic compounds, and their transformation products in wastewater from various treatment plants and the aquatic environment[J]. Science of the Total Environment, 2018, 640/641, 1015- 1023. doi: 10.1016/j.scitotenv.2018.05.218
26	Manickum T , John W . Occurrence, fate and environmental risk assessment of endocrine disrupting compounds at the wastewater treatment works in Pietermaritzburg(South Africa)[J]. Science of the Total Environment, 2014, 468/469, 584- 597. doi: 10.1016/j.scitotenv.2013.08.041
27	Zhou Haidong , Huang Xia , Wang Xiaolin , et al. Behaviour of selected endocrine-disrupting chemicals in three sewage treatment plants of Beijing, China[J]. Environmental Monitoring Assessment, 2010, 161 (1): 107- 121. URL
28	He Yujie , Chen Wei , Zheng Xiaoying , et al. Fate and removal of typical pharmaceuticals and personal care products by three different treatment processes[J]. Science of the Total Environment, 2013, 447, 248- 254. doi: 10.1016/j.scitotenv.2013.01.009
29	Sun Jie , Wang Jing , Zhang Rui , et al. Comparison of different advanced treatment processes in removing endocrine disruption effects from municipal wastewater secondary effluent[J]. Chemosphere, 2017, 168, 1- 9. doi: 10.1016/j.chemosphere.2016.10.031
30	Wu Qian , Lam J C W , Kwok K Y , et al. Occurrence and fate of endogenous steroid hormones, alkylphenol ethoxylates, bisphenol A and phthalates in municipal sewage treatment systems[J]. Journal of Environmental Sciences-China, 2017, 61, 49- 58. doi: 10.1016/j.jes.2017.02.021
31	Crisp T M , Clegg E D , Cooper R L , et al. Environmental endocrine disruption: An effects assessment and analysis[J]. Environmental Health Perspectives, 1998, 106 (S1): 11- 56. URL
32	Spindola Vilela C L , Bassin J P , Peixoto R S . Water contamination by endocrine disruptors: Impacts, microbiological aspects and trends for environmental protection[J]. Environmental Pollution, 2018, 235, 546- 559. doi: 10.1016/j.envpol.2017.12.098
33	Qin Chao , Shang Chao , Xia Kang . Removal of 17beta-estradiol from secondary wastewater treatment plant effluent using Fe(3+)-Saturated montmorillonite[J]. Chemosphere, 2019, 224, 480- 486. doi: 10.1016/j.chemosphere.2019.02.150
34	Oishi K , Moriuchi A . Removal of dissolved estrogen in sewage effluents by β-cyclodextrin polymer[J]. Science of the Total Environment, 2010, 409 (1): 112- 115. doi: 10.1016/j.scitotenv.2010.09.031
35	Ahmed M B , Zhou J L , Ngo H H , et al. Sorptive removal of phenolic endocrine disruptors by functionalized biochar: Competitive interaction mechanism, removal efficacy and application in wastewater[J]. Chemical Engineering Journal, 2018, 335, 801- 811. doi: 10.1016/j.cej.2017.11.041
36	Wang Liang , Liu Lu , Zhang Zhaohui , et al. 17α-Ethinylestradiol removal from water by magnetic ion exchange resin[J]. Chinese Journal of Chemical Engineering, 2018, 26 (4): 864- 869. doi: 10.1016/j.cjche.2017.08.006
37	Yoon Y , Westerhoff P , Snyder S A , et al. Removal of endocrine disrupting compounds and pharmaceuticals by nanofiltration and ultrafiltration membranes[J]. Desalination, 2007, 202 (1/2/3): 16- 23. URL
38	Xu Rui , Qin Wei , Zhang Bing , et al. Nanofiltration in pilot scale for wastewater reclamation: Long-term performance and membrane biofouling characteristics[J]. Chemical Engineering Journal, 2020, 395, 125087. doi: 10.1016/j.cej.2020.125087
39	Cunha G D S , Souza-Chaves B M , Bila D M , et al. Insights into estrogenic activity removal using carbon nanotube electrochemical filter[J]. Science of the Total Environment, 2019, 678, 448- 456. doi: 10.1016/j.scitotenv.2019.04.342
40	Ternes T A , Stuber J , Herrmann N , et al. Ozonation: A tool for removal of pharmaceuticals, contrast media and musk fragrances from wastewater?[J]. Water Research, 2003, 37 (8): 1976- 1982. doi: 10.1016/S0043-1354(02)00570-5
41	Nakagawa S , Kenmochi Y , Tutumi K , et al. A Study on the degradation of endocrine disruptors and dioxins by ozonation and advanced oxidation processes[J]. Journal of Chemical Engineering of Japan, 2002, 35 (9): 840- 847. doi: 10.1252/jcej.35.840
42	Hu Jianying , Cheng Shuijie , Aizawa T , et al. Products of aqueous chlorination of 17β-estradiol and their estrogenic activities[J]. Environmental Science & Technology, 2003, 37 (24): 5665- 5670. URL
43	Lee B , Kamata M , Akatsuka Y , et al. Effects of chlorine on the decrease of estrogenic chemicals[J]. Water Research, 2004, 38 (3): 733- 739. doi: 10.1016/j.watres.2003.10.010
44	Moriyama K , Matsufuji H , Chino M , et al. Identification and behavior of reaction products formed by chlorination of ethynylestradiol[J]. Chemosphere, 2004, 55 (6): 839- 847. doi: 10.1016/j.chemosphere.2003.11.045
45	Neval B , Li P G . Nanostructured catalysts for photo-oxidation of endocrine disrupting chemicals[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2018, 364, 274- 281. doi: 10.1016/j.jphotochem.2018.05.010
46	Wang Zijian , Sun Peizhe , Li Yaxiu , et al. Reactive nitrogen species mediated degradation of estrogenic disrupting chemicals by biochar/monochloramine in buffered water and synthetic hydrolyzed urine[J]. Environmental Science & Technology, 2019, 53 (21): 12688- 12696. URL
47	Zhang Peng , Tan Xiaofei , Liu Shaobo , et al. Catalytic degradation of estrogen by persulfate activated with iron-doped graphitic biochar: Process variables effects and matrix effects[J]. Chemical Engineering Journal, 2019, 378, 122- 141.
48	Angkaew A , Sakulthaew C , Satapanajaru T , et al. UV-activated persulfate oxidation of 17β-estradiol: Implications for discharge water remediation[J]. Journal of Environmental Chemical Engineering, 2019, 7 (2): 102858. URL
49	Cedat B , De Brauer C , Metivier H , et al. Are UV photolysis and UV/ H₂O₂ process efficient to treat estrogens in waters? Chemical and biological assessment at pilot scale[J]. Water Research, 2016, 100, 357- 366. doi: 10.1016/j.watres.2016.05.040
50	Huang Ying , Kong Minghao , Coffin S , et al. Degradation of contaminants of emerging concern by UV/H₂O₂ for water reuse: Kinetics, mechanisms, and cytotoxicity analysis[J]. Water Research, 2020, 174, 115587. doi: 10.1016/j.watres.2020.115587
51	Kumar A K , Mohan S V . Endocrine disruptive synthetic estrogen (17α-ethynylestradiol) removal from aqueous phase through batch and column sorption studies: Mechanistic and kinetic analysis[J]. Desalination, 2011, 276 (1): 66- 74.
52	Kumar A K , Mohan S V , Sarma P N . Sorptive removal of endocrinedisruptive compound(estriol, E3) from aqueous phase by batch and column studies: Kinetic and mechanistic evaluation[J]. Journal of Hazardous Materials, 2009, 164 (2): 820- 828.
53	Semiao A J C , Schafer A I . Estrogenic micropollutant adsorption dynamics onto nanofiltration membranes[J]. Journal of Membrane Science, 2011, 381 (1): 132- 141.
54	Koyuncu I , Arikan O A , Wiesner M R , et al. Removal of hormones and antibiotics by nanofiltration membranes[J]. Journal of Membrane Science, 2008, 309 (1/2): 94- 101. URL

化合物	分子式	摩尔质量/（g·mol^-1）	水中溶解度（20 ℃）/（mg·L^-1）	辛醇-水分配系数logK_ow	解离常数	雌激素效应相对值
雌酮（E1）	C₁₈H₂₂O₂	270	13	3.43	10.3~10.8	2.54
雌二醇（E2）	C₁₈H₂₄O₂	272	13	3.94	10.71	100
雌三醇（E3）	C₁₈H₂₄O₃	288	32	2.81	10.40	17.60
炔雌醇（EE2）	C₂₀H₂₄O₂	296	4.8	4.15	10.40	246.00

化合物	分子式	摩尔质量/（g·mol^-1）	水中溶解度（20 ℃）/（mg·L^-1）	辛醇-水分配系数logK_ow	解离常数	雌激素效应相对值
雌酮（E1）	C₁₈H₂₂O₂	270	13	3.43	10.3~10.8	2.54
雌二醇（E2）	C₁₈H₂₄O₂	272	13	3.94	10.71	100
雌三醇（E3）	C₁₈H₂₄O₃	288	32	2.81	10.40	17.60
炔雌醇（EE2）	C₂₀H₂₄O₂	296	4.8	4.15	10.40	246.00

化合物	取样地	最小质量浓度/（ng·L^-1）	最大质量浓度/（ng·L^-1）	平均质量浓度/（ng·L^-1）	参考文献
雌酮（E1）	灞河	2.40	55.90	17.46	〔14〕
	东洞庭湖	2.26	41.01	5.63	〔12〕
	洱海湖	4.70	55.00	14.40	〔15〕
	洪湖	ND	83.52	17.64	〔12〕
	辽河流域	2.60	1 235.00	66.20	〔9〕
	三峡库区	ND	52.30	10.53	〔10〕
	湘江	0.28	51.30	7.35	〔11〕
	沿海水域	ND	204.4	—	〔13〕
雌二醇（E2）	灞河	1.20	23.90	10.19	〔14〕
	东洞庭湖	ND	52.81	10.32	〔12〕
	洱海湖	1.10	17.40	5.06	〔15〕
	洪湖	ND	59.84	7.26	〔12〕
	辽河流域	2.60	1 254.00	45.30	〔9〕
	三峡库区	0.10	10.00	3.63	〔10〕
	湘江	0.28	46.20	10.92	〔11〕
	沿海水域	ND	ND	—	〔13〕
雌三醇（E3）	灞河	ND	5.20	1.42	〔14〕
	东洞庭湖	ND	66.67	20.69	〔12〕
	洱海湖	0.50	35.80	4.68	〔15〕
	洪湖	ND	56.35	27.70	〔12〕
	三峡库区	ND	81.60	17.35	〔10〕
	沿海水域	ND	278.4	—	〔13〕
炔雌醇（EE2）	灞河	ND	31.50	6.72	〔14〕
	东洞庭湖	ND	24.88	3.04	〔12〕
	洱海湖	0.50	16.10	3.03	〔15〕
	洪湖	ND	43.93	17.73	〔12〕
	辽河流域	2.60	17 112.00	596.00	〔9〕
	三峡库区	ND	35.30	7.87	〔10〕
	湘江	ND	21.40	5.37	〔11〕
	沿海水域	ND	120.7	—	〔13〕

化合物	取样地	最小质量浓度/（ng·L^-1）	最大质量浓度/（ng·L^-1）	平均质量浓度/（ng·L^-1）	参考文献
雌酮（E1）	灞河	2.40	55.90	17.46	〔14〕
	东洞庭湖	2.26	41.01	5.63	〔12〕
	洱海湖	4.70	55.00	14.40	〔15〕
	洪湖	ND	83.52	17.64	〔12〕
	辽河流域	2.60	1 235.00	66.20	〔9〕
	三峡库区	ND	52.30	10.53	〔10〕
	湘江	0.28	51.30	7.35	〔11〕
	沿海水域	ND	204.4	—	〔13〕
雌二醇（E2）	灞河	1.20	23.90	10.19	〔14〕
	东洞庭湖	ND	52.81	10.32	〔12〕
	洱海湖	1.10	17.40	5.06	〔15〕
	洪湖	ND	59.84	7.26	〔12〕
	辽河流域	2.60	1 254.00	45.30	〔9〕
	三峡库区	0.10	10.00	3.63	〔10〕
	湘江	0.28	46.20	10.92	〔11〕
	沿海水域	ND	ND	—	〔13〕
雌三醇（E3）	灞河	ND	5.20	1.42	〔14〕
	东洞庭湖	ND	66.67	20.69	〔12〕
	洱海湖	0.50	35.80	4.68	〔15〕
	洪湖	ND	56.35	27.70	〔12〕
	三峡库区	ND	81.60	17.35	〔10〕
	沿海水域	ND	278.4	—	〔13〕
炔雌醇（EE2）	灞河	ND	31.50	6.72	〔14〕
	东洞庭湖	ND	24.88	3.04	〔12〕
	洱海湖	0.50	16.10	3.03	〔15〕
	洪湖	ND	43.93	17.73	〔12〕
	辽河流域	2.60	17 112.00	596.00	〔9〕
	三峡库区	ND	35.30	7.87	〔10〕
	湘江	ND	21.40	5.37	〔11〕
	沿海水域	ND	120.7	—	〔13〕

取样点		进水质量浓度/（ng·L^-1）				出水质量浓度/（ng·L^-1）				参考文献
取样点		雌酮（E1）	雌二醇（E2）	雌三醇（E3）	炔雌醇（EE2）	雌酮（E1）	雌二醇（E2）	雌三醇（E3）	炔雌醇（EE2）	参考文献
国外	德国	66	22.7	—	—	14.6	4.6	—	—	〔21〕
	意大利	31	9.7	57	4.8	24	4	11.7	1.4	〔21〕
	英国	1.8~4.1	< 0.3	—	< LOD	< LOD	< LOD	—	< LOD	〔22〕
	西班牙	< 2.5~115	< 5~30.4	< 0.25~70.7	< 5	< 2.5~8.1	< 5~14.5	< 0.25~21.5	< 5	〔23〕
	法国	9.6~17.6	11.1~17.4	11.4~15.2	4.9~7.1	6.2~7.2	4.5~8.6	5.0~7.3	2.7~4.5	〔24〕
	韩国	17~224	5~31	83~3 660	—	3~23	ND	17~39	—	〔25〕
	南非	13~351	20~199	3~9	10~95	3~78	4~107	< 1	1~8	〔26〕
国内	北京	132.0~911.5	31.7~131.0	134.9~505.5	175.6~873.8	1.2~253.8	ND~64.3	ND~61.3	77.9~112.4	〔27〕
	昆明	50.1~154.3	8.4~40.2	23.4~70.7	7.5~42.3	1.4~62.5	ND~23.8	ND~17.3	ND~28.0	〔16〕
	江苏	29~129	1 126~1 170	53	2 193~4 437	7~18	41~101	39	280~549	〔28〕
	郑州	—	—	—	—	3.95± 0.64	4.68±0.89	—	0.24±0.07	〔29〕
	香港	11.0~33.1	1.6~3.3	14.5~113.8	ND	0.5~60.5	ND~1.6	ND~24.6	ND	〔30〕

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