2012—2021年中国地下水抗生素污染现状及分析技术研究进展

牛颖; 安圣; 陈凯; 秦久君; 刘菲

doi:10.15898/j.cnki.11-2131/td.202210120192

2012—2021年中国地下水抗生素污染现状及分析技术研究进展

1.
水利部地下水保护重点实验室(筹)，中国地质大学(北京)，北京 100083

2.
黑龙江省生态地质调查研究院，黑龙江哈尔滨，150028

基金项目:
国家自然科学基金项目“典型抗生素对地下水系统中反硝化过程的影响机理研究”(41731282)；广西省重点研发计划项目“桂林城区水土环境新型污染物防治关键技术研究与示范”(桂科AB22080070)

详细信息

作者简介: 牛颖，硕士研究生，研究方向为环境污染监测与评价。E-mail：15802242162@163.com

通讯作者: 刘菲，博士，教授，从事有机物污染监测与地下水污染治理研究工作。E-mail: feiliu@cugb.edu.cn

中图分类号: X502;O657.63

收稿日期: 2022-10-12

修回日期: 2022-11-29

录用日期: 2023-01-18

刊出日期: 2023-01-28

A Review of Current Status and Analysis Methods of Antibiotic Contamination in Groundwater in China (2012—2021)

1.
Key Laboratory of Groundwater Conservation of Ministry of Water Resources (in Preparation), China University of Geosciences (Beijing), Beijing 100083, China

2.
Heilongjiang Institute of Ecological Geological Survey, Haerbin 150028, China

More Information

Corresponding author: LIU Fei, feiliu@cugb.edu.cn

Received Date: 12 October 2022

Revised Date: 29 November 2022

Accepted Date: 18 January 2023

Publish Date: 28 January 2023

摘要

摘要:
抗生素作为一种新污染物，在不同环境介质中均有检出。未被人类或动物完全吸收和代谢的抗生素会通过废水和废弃物以原型或代谢产物的形式进入环境，并在土壤中积累或淋滤进入地下水。抗生素进入环境可能影响微生物生态, 产生抗性基因，甚至威胁人体健康，而地下水作为重要的饮用水源，其抗生素污染问题不容忽视。本文从抗生素的危害、使用情况、污染来源、污染现状、定性定量检测方法的优缺点及适应范围和形态分析及环境效应等方面对近十年来(2012—2021)中国地下水中抗生素的研究现状进行总结。经调查，中国常用28种抗生素检出浓度在0.1~1000ng/L以上，检出频率较高的抗生素为诺氟沙星、氧氟沙星、磺胺甲恶唑、恩诺沙星、磺胺嘧啶、红霉素等。从空间分布来看，对地下水中抗生素的研究主要集中在华北、西南地区，而对西北地区中地下水抗生素研究程度较低。目前为止受到分析方法检出限及检出种类的限制，对地下水中抗生素的调查及评价还不够全面。通过综述抗生素定性定量分析方法，发现HPLC-MS/MS法因其具有灵敏度高、选择性好和定性定量准确的优点是目前应用最广泛的抗生素定量分析方法，而且可利用该方法对环境中抗生素类型进行初步识别，针对主要类型开展定量分析或长期监测，为抗生素环境效应研究提供数据支撑。而当抗生素以不同的带电形态、络合形态、吸附形态存在时，因其理化性质不同会影响测定的准确性、环境行为和毒理学效应，因而开展抗生素的形态分析对进一步准确测定抗生素和评估其环境效应具有重要意义。本文认为，优化定性定量检测方法、分析抗生素的不同形态、全面调查地下水中抗生素和科学评价抗生素形态与生态毒理学效应的关系，是今后地下水中抗生素污染研究的重点课题。
- 地下水 /
- 抗生素 /
- 污染现状 /
- 环境行为 /
- 形态分析 /
- HPLC-MS/MS
Abstract:
As a form of new emerging pollutant, antibiotics have been detected in soil, surface water, groundwater, sediment and other different environmental media. As a major country in the production and usage of antibiotics, China's production and usage are increasing year by year. However, most antibiotics used for humans or animals cannot be fully absorbed and metabolized and will enter the environment in the form of prototypes or metabolites through waste and wastewater accumulating in soil and leaching into groundwater. Antibiotics entering the environment may affect microbial ecology, produce resistance genes, and even threaten human health. Compared with surface water, polluted groundwater is hidden, lagging and difficult to recover. The pollution of antibiotics in groundwater, as the main source of drinking water, has attracted much attention.

So far, the research on antibiotics in China is still mainly on surface water and soil, and there are few observations on antibiotics in groundwater. In order to systematically grasp the current pollution situation of antibiotics in groundwater in China, relevant literature on antibiotics in groundwater from 2012 to 2021 is reviewed in this paper. Twenty-eight antibiotics detected more than 100 times in environmental media in China were selected as target antibiotics, and the detected concentrations were summarized and analyzed. It was found that the concentrations of 28 antibiotics commonly detected in groundwater varied by more than 4 orders of magnitude, from 0.1ng/L to more than 1000ng/L. The most frequently detected antibiotics were norfloxacin, ofloxacin, sulfamethoxazole, sulfadiazine, enrofloxacin, and erythromycin. Through comparative analysis of the detection of antibiotics in various places, it can be seen that the concentration of antibiotics in groundwater is controlled by the properties of antibiotics, the location of pollution sources, hydrogeological structure and the amount of usage and emissions. From the perspective of spatial distribution, sulfonamide antibiotics are the most detected in northeast China, quinolones are the most detected in North and East China, quinolones and tetracyclines are the most detected in southwest China, and the research on antibiotics in groundwater in northwest China is relatively low. So far, restrained by the detection limits and detection types of the analysis methods, a comprehensive investigation and evaluation of antibiotics in groundwater is not possible.

Due to the wide variety of antibiotics, their different structures lead to different physical andchemical properties. They exist in trace concentrations in the complex environment media, which also affects the accuracy of their qualitative and quantitative analysis. Therefore, the establishment of a sensitive and specific multi-component simultaneous analysis method has been a key issue for antibiotics research. The analysis methods of antibiotics are summarized, which are divided into qualitative analysis methods and quantitative analysis methods. The principle, advantages, disadvantages and application range of several antibiotic analytical methods are presented. These methods include microbial inhibition method (MIT), thin layer chromatography (TLC), gas chromatogram-mass spectrometry (GC-MS), high-performance liquid chromatogram-nuclear magnetic resonance (HPLC-NMR) and liquid chromatogram-mass spectrometry (LC-MS). Liquid chromatogram-mass spectrometry (LC-MS) is the most commonly used method for antibiotic analysis because of its high sensitivity, low detection limit and simultaneous determination of multiple antibiotics. With the rapid development of antibiotic analysis methods, some antibiotics in groundwater can be accurately quantified by using HPLC-MS/MS and other technologies. However, the number of antibiotics that can be analyzed and identified at one time is still limited. The research group of authors has established the qualitative spectrum library of common drugs by UPLC-MS/MS. In the future, the types of antibiotics that can be qualitatively identified in the spectrum library can be expanded by adding the mass spectrum information of antibiotics. Under specific conditions, the spectrum library can be used to carry out semi-qualitative identification of antibiotics in groundwater. At present, the commonly used quantitative detection methods include enzyme-linked immunoassay, capillary electrophoresis, and liquid chromatography-mass spectrometry. Compared with the other two methods, liquid chromatography-mass spectrometry has the advantages of high sensitivity, good selectivity and accurate quantitative ability. It is commonly used for the detection of trace antibiotics in reported water samples.

Antibiotics exist in the environment at trace levels and the matrix of environmental samples is complex, so the pretreatment process, including antibiotic separation, purification and concentration, often becomes the key step of determination. For example, the samples to be tested should be adjusted to an appropriate pH to enhance the enrichment of target antibiotics on HLB columns, and Na₂EDTA should be added to inhibit its complexation with calcium and magnesium and other metal ions in groundwater. The accuracy of antibiotic determination will be improved, and the detection limit will be lowered for water samples by solid phase extraction and the subsequent concentration process. In addition to the detection limit and recovery rate of antibiotics affected by the analytical instrument, the presence states of antibiotics in water samples will also affect the accuracy and precision.

Antibiotics may exist in the ionized state, complex state, adsorption state and other forms in groundwater. At different pH values, antibiotics may exist in neutral, cationic, anionic, orzwitterionic forms. When it coexists with metal ions, complexation reaction will occur under certain conditions to form antibiotic-metal complex which will reduce the peak area to a certain extent or cause tailing phenomenon on the reverse analytical column. The formation of the complex may also change the environmental behavior (migration, transformation, toxicity, etc.) and ecological effects of antibiotics. In addition, the analysis of antibiotics in different adsorption states can be used to evaluate the differences in microbial killing effects of different adsorption forms, especially the differences in ARG production and spreading. This will be helpful for accurately evaluating the potential effects on the environment or human beings and effectively controlling the risks of antibiotics in environmental media. Therefore, the existing form analysis of antibiotics is of great significance for the further accurate determination of antibiotics and the evaluation of environmental effects.

Up to now, limited by the detection limits and detected types of antibiotics in analytical methods, there has not been a comprehensive national-scale investigation and evaluation of antibiotics in groundwater in China. Only by clarifying the concentration level and spatial distribution of antibiotic pollution in China's groundwater can it help to understand the contents of relevant laws and regulations on new emerging pollutants and support the establishment of a regulatory framework for natural resources and the environment. In conclusion, optimizing qualitative and quantitative detection methods, analyzing different existing forms of antibiotics, comprehensively investigating antibiotics in groundwater, and scientifically evaluating the relationship between antibiotic forms and ecotoxicological effects are the main contents of antibiotics research in groundwater in the future.
- groundwater /
- antibiotics /
- pollution status /
- environmental behavior /
- speciation analysis /
- HPLC-MS/MS

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图 1 地下水中抗生素的污染来源和迁移途径

Figure 1.

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图 2 中国地下水中28种常见抗生素的检出情况

Figure 2.

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图 3 不同种类抗生素在中国不同地区地下水中的检出情况

Figure 3.

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图 4 抗生素在地下水中的三种存在形式及形成机理

Figure 4.

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图 5 (a) 四环素类抗生素结构式及(b)四环素在水中随pH变化的物质形态分布

Figure 5.

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图 6 抗生素与水中金属共存的作用机理

Figure 6.

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表 1 抗生素定性方法

Table 1. Qualitative methods for antibiotics analysis

抗生素定性方法	方法原理	方法优缺点	方法适用范围
微生物抑制法 (Microbial Inhibition Technique，MIT)	传统的测定方法，利用抗生素对微生物的生理机能、代谢的抑制作用，与阴性对照进行对比，判断是否存在抗生素^[60]	操作简单，但灵敏度低，特异性差，且相似抗生素之间干扰性大^[61]	动物性食品中抗生素残留^[62]
薄层色谱法 (Thin Layer Chromatography，TLC)	利用各成分对同一吸附剂吸附能力不同，从而达到各成分相互分离的目的	具有设备简单、操作简便等优点^[63]，但样品处理复杂，且灵敏度低^[64]	可用于快速分离和定性少量分析物质
气相色谱-质谱联用 (Gas Cluomatography- Mass Spectrometry，GC-MS)	利用样品在色谱柱中气相和固定相间分配系数的不同，经过反复多次分配从而实现分离^[65]	具有稳定性好、重复性强、操作简单和扩容性强及普适性大等优点，但不适用于极性大、难挥发的有机污染物^[59]	应用于农药和易挥发性有机污染物的定性检测
高效液相色谱-核磁共振联用 (HPLC-NMR)	利用HPLC分离复杂化合物，NMR波谱确证未知化合物的结构^[66]	该方法相较于质谱检测技术，灵敏度较低，且分析成本高	可用于分析化合物的组成、结构及其变化规律，被广泛应用于化学、医学等行业^[67]

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表 2 常见抗生素的酸解离常数及存在形式

Table 2. Acid dissociation constants and existing forms of common antibiotics

抗生素类别	抗生素名称	pKa	pH范围	抗生素形式	参考文献
四环素类	四环素 (TC)	pKa₁=3.3	＜3.30	H₃TC⁺	[94]
		pKa₂=7.7	3.30~7.70	HTC^-/TC^2-
		pKa₃=9.7	＞7.70	HTC^-/TC^2-
磺胺类	磺胺噻唑 (STZ)	pKa₁=2.0 pKa₂=7.24	＜2.00	STZ⁺	[95]
			2.00~7.24	STZ⁰
			＞7.24	STZ^-
大环内酯类	罗红霉素 (ROX)	pKa₁=9.08 pKa₂=12.45	＜9.08	ROX⁺	[96]
			9.08~12.45	ROX⁰
			＞12.45	ROX^-
β-内酰胺类	头孢拉定 (CED)	pKa₁=2.63 pKa₂=7.27	＜2.63	CED⁺	[97]
			2.63~7.27	CED⁰
			＞7.27	CED^-
喹诺酮类	环丙沙星 (CIP)	pKa₁=6.1 pKa₂=8.7	＜6.10	CIP⁺	[98]
			6.10~8.70	CIP⁰
			＞8.70	CIP^-

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