Research progress of metformin removal process in water environment

doi:10.19965/j.cnki.iwt.2021-0752

Abstract

Abstract:

Metformin（MET） has been widely used for treating type Ⅱ diabetes all over the world. The annual consumption of MET by Chinese has been gradually increased since 1980. MET can’t be metabolized by human being，thus about 70% of the intake MET was excreted unchanged through the body fluids，thus occurred in the domestic wastewater and finally entered into the wastewater treatment plants. Due to its stable molecular structure，it is hard to be removed by conventional water treatment technology，consequently which is detected in various environmental media. Based on the relevant literatures at home and abroad，the occurrence of MET in many environmental media including wastewater，surface water and drinking water was summarized. Besides，the frequently-used analytical methods for detecting MET in environmental water samples including sample pretreatment methods like solid phase extraction（SPE） and instrumental analytical methods such as ultra-high performance liquid chromatography coupled with mass spectrum（UPLC-MS/MS），gas chromatography coupled with mass spectrum（GC/MS） were concluded. Finally，MET removal technologies were elucidated from three aspects including physical，biological and chemical methods. Amongst them，chemical methods represented by advanced oxidation processes（AOPs）（mainly including ozonation，chlorination，electro-oxidation and photo-oxidation methods） have been extensively explored for MET removal. Various AOPs were compared in the aspects of removal efficiency，reaction mechanisms and influential factors to evaluate their application prospect in MET removal. Additionally，future research direction on MET removal technology was proposed.

Key words: metformin, current situation of pollution, analytical methods, removal techniques

摘要：

二甲双胍（MET）是治疗Ⅱ型糖尿病的常用药物，在世界范围内被广泛使用。自1980年以来，国内MET使用量逐年增加。MET无法被人体代谢，经患者口服之后，约70%的MET会以体液形式排出体外，随生活污水进入污水处理厂。MET结构稳定，常规水处理工艺对其去除效果有限，因而在多种环境介质中均检测出含有MET。基于国内外相关文献，总结了MET在污（废）水、地表水及饮用水等环境介质中的浓度水平。在此基础上归纳了MET在环境水样检测中常用的分析方法，包括固相萃取（SPE）样品前处理方法、以及高效液相色谱串联质谱（HPLC-MS/MS）、气相色谱串联质谱（GC/MS）等仪器分析方法。最后，从物理、生物及化学法三方面阐述了当前水体中MET的主要去除技术。其中，以高级氧化技术为代表的化学法去除MET被广泛研究，主要分为臭氧氧化、氯氧化、电化学氧化以及光化学氧化四类。最后从去除效能、反应机理和影响因素等方面比较了各高级氧化技术在MET去除方面的应用前景，并对今后的研究方向进行展望。

关键词: 二甲双胍, 污染现状, 分析方法, 去除工艺

CLC Number:

X703

Hongxing SONG, Meifen CHEN, Zijun DONG, Yurong GU. Research progress of metformin removal process in water environment[J]. Industrial Water Treatment, 2022, 42(9): 1-7.

宋洪星, 陈梅芬, 董紫君, 顾玉蓉. 水环境中的二甲双胍及其去除工艺研究进展[J]. 工业水处理, 2022, 42(9): 1-7.

/ / Recommend / Download Citations

URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2021-0752

https://www.iwt.cn/EN/Y2022/V42/I9/1

Figures/Tables 5

References 42

1	BESSE J P， GARRIC J. Human pharmaceuticals in surface waters：Implementation of a priori tization methodology and application to the French situation［J］. Toxicology Letters，2008，176（2）：104-123. doi:10.1016/j.toxlet.2007.10.012
2	BADRAN I， MANASRAH A D， NASSAR N N. A combined experimental and density functional theory study of metformin oxy-cracking for pharmaceutical wastewater treatment［J］. RSC Advances，2019，9（24）：13403-13413. doi:10.1039/c9ra01641d
3	Federation I D. IDF Diabetes Atlas，eighth Edition［R］. Brussels：International Diabetes Federation，2017.
4	CHEN Chang， KOSTAKIS C， IRVINE R J，et al. Evaluation of pre-analysis loss of dependent drugs in wastewater：Stability and binding assessments［J］. Drug Testing and Analysis，2013，5（8）：716-721. doi:10.1002/dta.1428
5	YAN Jihao， XIAO Yang， TAN Dongqin，et al. Wastewater analysis reveals spatial pattern in consumption of anti-diabetes drug metformin in China［J］. Chemosphere，2019，222：688-695. doi:10.1016/j.chemosphere.2019.01.151
6	SCHEURER M， MICHEL A， BRAUCH H J，et al. Occurrence and fate of the antidiabetic drug metformin and its metabolite guanylurea in the environment and during drinking water treatment［J］. Water Research，2012，46（15）：4790-4802. doi:10.1016/j.watres.2012.06.019
7	AMBROSIO-ALBUQUERQUE E P， CUSIOLI L F， BERGAMASCO R，et al. Metformin environmental exposure：A systematic review［J］. Environmental Toxicology and Pharmacology，2021，83：103588. doi:10.1016/j.etap.2021.103588
8	HUBER S， REMBERGER M，KAJ L，et al. A first screening and risk assessment of pharmaceuticals and additives in personal care products in waste water，sludge，recipient water and sediment from Faroe Islands，Iceland and Greenland［J］. Science of the Total Environment，2016，562：13-25. doi:10.1016/j.scitotenv.2016.03.063
9	NIEMUTH N J， KLAPER R D. Emerging wastewater contaminant metformin causes intersex and reduced fecundity in fish［J］. Chemosphere，2015，135：38-45. doi:10.1016/j.chemosphere.2015.03.060
10	DE JESUS GAFFNEY V， CARDOSO V V， CARDOSO E，et al. Occurrence and behaviour of pharmaceutical compounds in a Portuguese wastewater treatment plant：Removal efficiency through conventional treatment processes［J］. Environmental Science and Pollution Research International，2017，24（17）：14717-14734. doi:10.1007/s11356-017-9012-7
11	SANTOS L H M L M， GROS M， RODRIGUEZ-MOZAZ S，et al. Contribution of hospital effluents to the load of pharmaceuticals in urban wastewaters：Identification of ecologically relevant pharmaceuticals［J］. Science of the Total Environment，2013，461/462：302-316. doi:10.1016/j.scitotenv.2013.04.077
12	TRAUTWEIN C， BERSET J D， WOLSCHKE H，et al. Occurrence of the antidiabetic drug Metformin and its ultimate transformation product Guanylurea in several compartments of the aquatic cycle［J］. Environment International，2014，70：203-212. doi:10.1016/j.envint.2014.05.008
13	SCHEURER M， SACHER F， BRAUCH H J. Occurrence of the antidiabetic drug metformin in sewage and surface waters in Germany［J］. Journal of Environmental Monitoring：JEM，2009，11（9）：1608-1613. doi:10.1039/b909311g
14	KONG Lingxiao， KADOKAMI K， WANG Shaopo，et al. Monitoring of 1 300 organic micro-pollutants in surface waters from Tianjin，North China［J］. Chemosphere，2015，122：125-130. doi:10.1016/j.chemosphere.2014.11.025
15	KOT-WASIK A， JAKIMSKA A， ŚLIWKA-KASZYŃSKA M. Occurrence and seasonal variations of 25 pharmaceutical residues in wastewater and drinking water treatment plants［J］. Environmental Monitoring and Assessment，2016，188（12）：661. doi:10.1007/s10661-016-5637-0
16	KOSMA C I， LAMBROPOULOU D A， ALBANIS T A. Comprehensive study of the antidiabetic drug metformin and its transformation product guanylurea in Greek wastewaters［J］. Water Research，2015，70：436-448. doi:10.1016/j.watres.2014.12.010
17	KIM M， GUERRA P， SHAH A，et al. Removal of pharmaceuticals and personal care products in a membrane bioreactor wastewater treatment plant［J］. Water Science and Technology：A Journal of the International Association on Water Pollution Research，2014，69（11）：2221-2229. doi:10.2166/wst.2014.145
18	MARTÍN J， BUCHBERGER W， SANTOS J L，et al. High-performance liquid chromatography quadrupole time-of-flight mass spectrometry method for the analysis of antidiabetic drugs in aqueous environmental samples［J］. Journal of Chromatography B，2012，895/896：94-101. doi:10.1016/j.jchromb.2012.03.023
19	SHRAIM A， DIAB A， ALSUHAIMI A，et al. Analysis of some pharmaceuticals in municipal wastewater of almadinah almunawarah［J］. Arabian Journal of Chemistry，2017，10：S719-S729. doi:10.1016/j.arabjc.2012.11.014
20	BLAIR B D， CRAGO J P， HEDMAN C J，et al. Pharmaceuticals and personal care products found in the Great Lakes above concentrations of environmental concern［J］. Chemosphere，2013，93（9）：2116-2123. doi:10.1016/j.chemosphere.2013.07.057
21	ELLIOTT S M， VANDERMEULEN D D. A regional assessment of chemicals of concern in surface waters of four Midwestern United States National Parks［J］. Science of the Total Environment，2017，579：1726-1735. doi:10.1016/j.scitotenv.2016.11.114
22	CARMONA E， ANDREU V， PICÓ Y. Multi-residue determination of 47 organic compounds in water，soil，sediment and fish—Turia River as case study［J］. Journal of Pharmaceutical and Biomedical Analysis，2017，146：117-125. doi:10.1016/j.jpba.2017.08.014
23	ALI A M， RØNNING H T， ALARIF W，et al. Occurrence of pharmaceuticals and personal care products in effluent-dominated Saudi Arabian coastal waters of the Red Sea［J］. Chemosphere，2017，175：505-513. doi:10.1016/j.chemosphere.2017.02.095
24	HOUTMAN C J， KROESBERGEN J， LEKKERKERKER-TEUNISSEN K，et al. Human health risk assessment of the mixture of pharmaceuticals in Dutch drinking water and its sources based on frequent monitoring data［J］. Science of the Total Environment，2014，496：54-62. doi:10.1016/j.scitotenv.2014.07.022
25	QUINTÃO F J O， FREITAS J R L， DE FÁTIMA MACHADO C，et al. Characterization of metformin by-products under photolysis，photocatalysis，ozonation and chlorination by high-performance liquid chromatography coupled to high-resolution mass spectrometry［J］. Rapid Communications in Mass Spectrometry，2016，30（21）：2360-2368. doi:10.1002/rcm.7724
26	许秋月，陈贝贝，何蔓，等. 基于巯基功能化磁球的磁固相萃取-ICP-MS联用用于环境水样中无机砷形态分析［J］. 分析测试学报，2021，40（6）：954-959. doi:10.3969/j.issn.1004-4957.2021.06.023
	XU Qiuyue， CHEN Beibei， HE Man，et al. Speciation analysis of inorganic arsenic in environmental water samples by ICP-MS with magnetic solid phase extraction based on sulfhydryl functionalized magnetic sorbents［J］. Journal of Instrumental Analysis，2021，40（6）：954-959. doi:10.3969/j.issn.1004-4957.2021.06.023
27	MAĆERAK A L， KERKEZ Đ， BEČELIĆ-TOMIN M，et al. Removal of diclofenac and metformin from water in laboratory photo reactor［C］//Environment，Green Technology，and Engineering International Conference. Basel Switzerland：MDPI，2018.
28	ZHU Shuai， LIU Yunguo， LIU Shaobo，et al. Adsorption of emerging contaminant metformin using graphene oxide［J］. Chemosphere，2017，179：20-28. doi:10.1016/j.chemosphere.2017.03.071
29	ALNAJJAR M， HETHNAWI A， NAFIE G，et al. Silica-alumina composite as an effective adsorbent for the removal of metformin from water［J］. Journal of Environmental Chemical Engineering，2019，7（3）：102994. doi:10.1016/j.jece.2019.102994
30	POURSAT B A J， VAN SPANNING R J M， BRASTER M，et al. Biodegradation of metformin and its transformation product，guanylurea，by natural and exposed microbial communities［J］. Ecotoxicology and Environmental Safety，2019，182：109414. doi:10.1016/j.ecoenv.2019.109414
31	TRAUTWEIN C， KÜMMERER K. Incomplete aerobic degradation of the antidiabetic drug Metformin and identification of the bacterial dead-end transformation product Guanylurea［J］. Chemosphere，2011，85（5）：765-773. doi:10.1016/j.chemosphere.2011.06.057
32	BRIONES R M， ZHUANG Weiqin， SARMAH A K. Biodegradation of metformin and guanylurea by aerobic cultures enriched from sludge［J］. Environmental Pollution，2018，243：255-262. doi:10.1016/j.envpol.2018.08.075
33	MAO Yuanxiang， DONG Huiyu， LIU Shaogang，et al. Accelerated oxidation of iopamidol by ozone/peroxymonosulfate（O₃/PMS） process：Kinetics，mechanism，and simultaneous reduction of iodinated disinfection by-product formation potential［J］. Water Research，2020，173：115615. doi:10.1016/j.watres.2020.115615
34	JIN Xiaohui， PELDSZUS S， HUCK P M. Reaction kinetics of selected micropollutants in ozonation and advanced oxidation processes［J］. Water Research，2012，46（19）：6519-6530. doi:10.1016/j.watres.2012.09.026
35	MUÑOZ F， VON SONNTAG C. The reactions of ozone with tertiary amines including the complexing agents nitrilotriacetic acid（NTA） and ethylenediaminetetraacetic acid（EDTA） in aqueous solution［J］. Journal of the Chemical Society，Perkin Transactions 2，2000（10）：2029-2033. doi:10.1039/b004417m
36	HUBER M M， KORHONEN S， TERNES T A，et al. Oxidation of pharmaceuticals during water treatment with chlorine dioxide［J］. Water Research，2005，39（15）：3607-3617. doi:10.1016/j.watres.2005.05.040
37	ASEMAN-BASHIZ E， SAYYAF H. Metformin degradation in aqueous solutions by electro-activation of persulfate and hydrogen peroxide using natural and synthetic ferrous ion sources［J］. Journal of Molecular Liquids，2020，300：112285. doi:10.1016/j.molliq.2019.112285
38	WOLS B A， HARMSEN D J H， BEERENDONK E F，et al. Predicting pharmaceutical degradation by UV（LP）/H₂O₂ processes：A kinetic model［J］. Chemical Engineering Journal，2014，255：334-343. doi:10.1016/j.cej.2014.05.088
39	DE LA CRUZ N， GIMÉNEZ J， ESPLUGAS S，et al. Degradation of 32 emergent contaminants by UV and neutral photo-Fenton in domestic wastewater effluent previously treated by activated sludge［J］. Water Research，2012，46（6）：1947-1957. doi:10.1016/j.watres.2012.01.014
40	KARIMIAN S， MOUSSAVI G， FANAEI F，et al. Shedding light on the catalytic synergies between Fe（Ⅱ） and PMS in vacuum UV（VUV/Fe/PMS） photoreactors for accelerated elimination of pharmaceuticals：The case of metformin［J］. Chemical Engineering Journal，2020，400：125896. doi:10.1016/j.cej.2020.125896
41	CARBULONI C F， SAVOIA J E， SANTOS J S P，et al. Degradation of metformin in water by TiO₂-ZrO₂ photocatalysis［J］. Journal of Environmental Management，2020，262：110347. doi:10.1016/j.jenvman.2020.110347
42	ORSETTI F R， BUKMAN L， SANTOS J S，et al. Methylene blue and metformin photocatalytic activity of CeO₂-Nb₂O₅ coatings is dependent on the treatment time of plasma electrolytic oxidation on titanium［J］. Applied Surface Science Advances，2021，6：100143. doi:10.1016/j.apsadv.2021.100143

国家	样品来源	进水MET/（μg·L^-1）	出水MET/（μg·L^-1）	参考文献
葡萄牙	市政废水	70~325	0.05~58	〔10〕
葡萄牙	市政废水	n.d~1.568	0.003 87~0.299	〔11〕
德国	市政废水	86.2~142.3	3.4~6.4	〔12〕
德国	市政废水	101~129	2.2~21	〔13〕
北欧	市政废水	1.79~59	0.234~7.95	〔8〕
中国	市政废水	2.42~53.6	—	〔5〕
中国	市政废水	—	n.d~20.015	〔14〕
波兰	市政废水	3.818~16.79	0.007 5~0.062 9	〔15〕
希腊	市政废水	n.d~1.167	n.d~0.026	〔16〕
加拿大	市政废水	—	0.5	〔17〕
澳大利亚	市政废水	—	0.253	〔18〕
沙特阿拉伯	市政废水	4.02~31.2	n.d~4.51	〔19〕
美国	市政废水	—	1.2~3.8	〔20〕

国家	样品来源	进水MET/（μg·L^-1）	出水MET/（μg·L^-1）	参考文献
葡萄牙	市政废水	70~325	0.05~58	〔10〕
葡萄牙	市政废水	n.d~1.568	0.003 87~0.299	〔11〕
德国	市政废水	86.2~142.3	3.4~6.4	〔12〕
德国	市政废水	101~129	2.2~21	〔13〕
北欧	市政废水	1.79~59	0.234~7.95	〔8〕
中国	市政废水	2.42~53.6	—	〔5〕
中国	市政废水	—	n.d~20.015	〔14〕
波兰	市政废水	3.818~16.79	0.007 5~0.062 9	〔15〕
希腊	市政废水	n.d~1.167	n.d~0.026	〔16〕
加拿大	市政废水	—	0.5	〔17〕
澳大利亚	市政废水	—	0.253	〔18〕
沙特阿拉伯	市政废水	4.02~31.2	n.d~4.51	〔19〕
美国	市政废水	—	1.2~3.8	〔20〕

国家	样品来源	MET质量浓度/质量分数	参考文献
美国	地表水	0.11~9.2 μg/L	〔20〕
美国	地表水	0.1~0.903 μg/L	〔21〕
越南	地表水	7 μg/L	〔14〕
德国	地表水	0.035~0.643 μg/L	〔12〕
西班牙	地表水	<0.025 μg/L	〔22〕
沙特阿拉伯	地表水	4.801 μg/L	〔23〕
北欧	地表水	<0.002 08~0.748 μg/L	〔8〕
德国	饮用水	0.002~0.061 μg/L	〔12〕
荷兰	饮用水	0.026~0.031 μg/L	〔24〕
美国	沉积物	2.3~140 ng/g	〔20〕
北欧	沉积物	<0.50~56.7 μg/kg	〔8〕
北欧	污泥	7 810 μg/kg	〔8〕

国家	样品来源	MET质量浓度/质量分数	参考文献
美国	地表水	0.11~9.2 μg/L	〔20〕
美国	地表水	0.1~0.903 μg/L	〔21〕
越南	地表水	7 μg/L	〔14〕
德国	地表水	0.035~0.643 μg/L	〔12〕
西班牙	地表水	<0.025 μg/L	〔22〕
沙特阿拉伯	地表水	4.801 μg/L	〔23〕
北欧	地表水	<0.002 08~0.748 μg/L	〔8〕
德国	饮用水	0.002~0.061 μg/L	〔12〕
荷兰	饮用水	0.026~0.031 μg/L	〔24〕
美国	沉积物	2.3~140 ng/g	〔20〕
北欧	沉积物	<0.50~56.7 μg/kg	〔8〕
北欧	污泥	7 810 μg/kg	〔8〕

Please choose a citation manager

Content to export