钱塘江流域杭州段地表水中典型抗生素的分布特征及生态风险评价

叶旭红; 张宝锋; 周猛; 何平; 刘子述; 冒冉; 叶永根; 朱英俊; 陈峰

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中国环境科学 ›› 2024, Vol. 44 ›› Issue (6) : 3247-3258.

水污染与控制

钱塘江流域杭州段地表水中典型抗生素的分布特征及生态风险评价

叶旭红¹, 张宝锋¹, 周猛², 何平¹, 刘子述², 冒冉³, 叶永根¹, 朱英俊¹, 陈峰¹

作者信息 +

Distribution characteristics and ecological risk evaluation of typical antibiotics in surface water of Hangzhou section of the Qiantang River basin

YE Xu-hong¹, ZHANG Bao-feng¹, ZHOU Meng², HE Ping¹, LIU Zi-shu², MAO Ran³, YE Yong-gen¹, ZHU Ying-jun¹, CHEN Feng¹

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摘要

采用固相萃取和超高效液相色谱-串联质谱法(LC-MS/MS)首次测定钱塘江流域杭州段地表水中β-内酰胺类(β-Ls)、喹诺酮类(QNs)、磺胺类(SAs)、大环内酯类(MLs)、四环素类(TCs)、广谱抗菌药物(WAs)等6类83种典型抗生素的浓度水平,初步探明钱塘江流域杭州段中典型抗生素的区域分布特征,并利用风险熵值法评价了抗生素赋存的潜在风险.结果表明,46种抗生素在钱塘江流域杭州段有检出,地表水中抗生素总平均浓度在枯水期、平水期、丰水期分别为27.8, 24.8, 23.8ng/L,枯水期抗生素浓度略高于平水期和丰水期,且抗生素总检出浓度呈现上游＞中游＞下游的趋势.其中,林可霉素(LCM)的检出率高达 98.2%,最高检出浓度为22.7ng/L,平均浓度与中位浓度分别为8.04ng/L和8.14ng/L,是区域地表水中的特征抗生素.其他检出率较高的抗生素有磺胺甲噁唑(SMX)、磺胺氯哒嗪(SCP)、甘宝素(CB)、甲氧苄氨嘧啶(TMP)、氟康唑(FCZ)、磺胺(SM)、克拉霉素(CLT)等,其平均浓度分别为3.60,2.56,1.07,0.97,1.09,1.08,0.70ng/L.主成分分析结果显示LCM、SMX、SM、SCP的浓度变化与其他抗生素有相比有显著差异.生态风险评价结果表明,钱塘江流域杭州段所有检出抗生素单项生态风险熵(RQ)均小于1.0,未发现高生态风险抗生素.

Abstract

The concentration of 83 typical antibiotics in surface water of the Hangzhou section of the Qiantang River basin were determined by solid-phase extraction and Ultra performance liquid chromatography tandem triple quadrupole mass spectrometry (UPLC-MS/MS) for the first time, including β-lactams (β-Ls), quinolones (QNs), sulfonamides (SAs), macrolides (MLs), tetracyclines (TCs), and broad-spectrum antibacterial drugs (WAs). The regional distribution characteristics of typical antibiotics in the Hangzhou section of the Qiantang River were preliminarily investigated. The potential risks of antibiotic occurrence were evaluated using the risk entropy method. The results indicated that 46types of antibiotics were detected in the Hangzhou section of the Qiantang River basin. The overall average concentrations of antibiotics in surface water during the dry season, normal water level period, and flood season were 27.8, 24.8, and 23.8ng/L, respectively. The antibiotic concentration during the dry season was slightly higher than that during the normal water level period and flood season, and the total detected antibiotic concentrations exhibited a trend of upstream > midstream > downstream. Among them, lincomycin (LCM) was detected at a high rate of 98.2%, with the highest detected concentration of 22.7ng/L and the mean and median concentrations of 8.04ng/L and 8.14ng/L, respectively, making it a characteristic antibiotic in regional surface water. Sulfamethoxazole (SMX), Sulfachloropyridazine (SCP), Climbazole (CB), Trimethoprim (TMP), Fluconazole (FCZ), Sulfonamide (SM), Clarithromycin (CLT) were the second most frequently detected antibiotics, with the average concentrations of 3.60, 2.56, 1.07, 0.97, 1.09, 1.08, 0.70ng/L, respectively. The results of principal component analysis showed that the concentration changes of LCM, SMX, SM and SCP were significantly different compared with other antibiotics. Ecological risk assessment results indicated that the single ecological risk quotient (RQ) of all detected antibiotics in the Hangzhou section of the Qiantang River basin was less than 1.0, suggesting the absence of high ecological risk antibiotics.

导出引用

叶旭红, 张宝锋, 周猛, 何平, 刘子述, 冒冉, 叶永根, 朱英俊, 陈峰. 钱塘江流域杭州段地表水中典型抗生素的分布特征及生态风险评价[J]. 中国环境科学. 2024, 44(6): 3247-3258

YE Xu-hong, ZHANG Bao-feng, ZHOU Meng, HE Ping, LIU Zi-shu, MAO Ran, YE Yong-gen, ZHU Ying-jun, CHEN Feng. Distribution characteristics and ecological risk evaluation of typical antibiotics in surface water of Hangzhou section of the Qiantang River basin[J]. China Environmental Science. 2024, 44(6): 3247-3258

中图分类号： X53

参考文献

[1] 陈昱如,段艳平,张智博,等.长江经济带水环境中抗生素人体健康风险评价[J].中国环境科学, 2023,43(7):3713-3729. Chen Y, Duan Y P, Zhang Z B, et al. Human health risk assessment of antibiotics in the water environment of the Yangtze River Economic Belt[J]. China Environmental Science, 2023,43(7):3713-3729.
[2] 邢月,张雯,程艳,等.西北内陆河抗生素抗性基因赋存特征及其影响因素[J].中国环境科学, 2023,43(6):3077-3086. Xing Y, Zhang W, Cheng Y, et al. Characteristics of antibiotic resistance genes and their influencing factors in the Northwest Inland Rivers[J]. China Environmental Science, 2023,43(6):3077-3086.
[3] P Lu, Y Fang, J B Barvor, et al. Review of antibiotic pollution in the seven watersheds in China[J]. Polish Journal of Environmental Studies, 2019,28(6):4045-4055.
[4] A J Browne, M G Chipeta, G Haines-Woodhouse, et al. Global antibiotic consumption and usage in humans, 2000~2018:a spatial modelling study[J]. The Lancet Planetary Health, 2021,5(12):893-904.
[5] Pavla Kovalakova, Leslie Cizmas, Thomas J, et al. Occurrence and toxicity of antibiotics in the aquatic environment:A review[J]. Chemosphere, 2020,251:126351.
[6] V K Sharma, N Johnson, L Cizmas, et al. A review of the influence of treatment strategies on antibiotic resistant bacteria and antibiotic resistance genes[J]. Chemosphere, 2016,150:702-714.
[7] C Jin,S Wei,R Sun, et al. The forms, distribution, and risk assessment of sulfonamide antibiotics in the manure-soil-vegetable system of feedlot livestock[J]. Bulletin of Environmental Contamination and Toxicology, 2020,105(5):790-797.
[8] M Li, L Yang, H Yen, et al. Occurrence, spatial distribution and ecological risks of antibiotics in soil in urban agglomeration[J]. Journal of Environmental Sciences, 2023,125:678-690.
[9] F Zhao, L Chen, L Yang, et al. Effects of land use and rainfall on sequestration of veterinary antibiotics in soils at the hillslope scale[J]. Environmental Pollution, 2020,260:114112.
[10] S Moles, S Gozzo, M P Ormad, et al. Long-term study of antibiotic presence in ebro river basin (Spain):identification of the emission sources[J]. Water, 2022,14(7):1033.
[11] M Bilal, S Mehmood, T Rasheed, et al. Antibiotics traces in the aquatic environment:persistence and adverse environmental impact[J]. Current Opinion in Environmental Science&Health, 2020,13:68-74.
[12] N Ma, L Tong, Y Li, et al. Distribution of antibiotics in lake water-groundwater-Sediment system in Chenhu Lake area[J]. Environmental Research, 2022,204:112343.
[13] F Li, L Chen, W Chen, et al. Antibiotics in coastal water and sediments of the East China Sea:Distribution, ecological risk assessment and indicators screening[J]. Marine Pollution Bulletin, 2020,151:110810.
[14] Z Yin. Distribution and ecological risk assessment of typical antibiotics in the surface waters of seven major rivers, China[J]. Environ Sci Process Impacts, 2021,23(8):1088-1100.
[15] 李佳乐,王萌,胡发旺.江西锦江流域抗生素污染特征与生态风险评价[J].环境科学, 2022,43(8):4064-4073. Li J L, Wang M, Hu F W. Characteristics of antibiotic pollution and ecological risk assessment in the Jinjiang River Basin, Jiangxi Province[J]. Environmental Science, 2022,43(8):4064-4073.
[16] M Kong, L Xing, R Yan, et al. Spatiotemporal variations and ecological risks of typical antibiotics in rivers inflowing into Taihu Lake, China[J]. J Environ Manage, 2022,309:114699.
[17] 张晶晶,陈娟,王沛芳,等.中国典型湖泊四大类抗生素污染特征[J].中国环境科学, 2021,41(9):4271-4283. Zhang J J, Chen J, Wang P F, et al. Characteristics of antibiotic pollution in four typical lakes in China[J]. China Environmental Science, 2021,41(9):4271-4283.
[18] S Li, W Z Shi, M T You, et al. Antibiotics in water and sediments of Danjiangkou Reservoir, China:Spatiotemporal distribution and indicator screening[J]. Environmental Pollution, 2019,246:435-442.
[19] 卢诚,张俊,王钊,等.河北潘家口水库氯霉素类抗生素检测及风险评估[J].中国环境科学, 2016,36(6):1843-1849. Lu C, Zhang J, Wang Z, et al. Detection and risk assessment of chloramphenicol antibiotics in the Panjiakou Reservoir in Hebei Province[J]. China Environmental Science, 2016,36(6):1843-1849.
[20] 弥启欣,国晓春,卢少勇.千岛湖水体中邻苯二甲酸酯(PAEs)的分布特征及健康风险评价[J].环境科学, 2022,43(4):1966-1975. Mi Q, Guo X C, Lu S Y. Distribution characteristics of phthalate esters (PAEs) in the water of Qiandao Lake and health risk assessment[J]. Environmental Science, 2022,43(4):1966-1975.
[21] 李桂娥,李杰,赵冲,等.生态系统服务时空演化的非线性影响因子--以钱塘江流域为例[J].中国环境科学, 2022,42(12):5941-5952. Li G E, Li J, Zhao C, et al. Nonlinear influencing factors of spatiotemporal evolution of ecosystem services:A case study of the Qiantang River basin[J]. China Environmental Science, 2022,42(12):5941-5952.
[22] Fabregat Safont D, Gracia Marín E, Ibáñez M, et al. Analytical key issues and challenges in the LC-MS/MS determination of antibiotics in wastewater[J]. Analytica Chimica Acta, 2023,1239:340739.
[23] Mostafa A, Shaaban H, Alqarni A, et al. Multi-class determination of pharmaceuticals as emerging contaminants in wastewater from Eastern Province, Saudi Arabia using eco-friendly SPE-UHPLC-MS/MS:Occurrence, removal and environmental risk assessment[J]. Microchemical Journal, 2023,187:108453.
[24] Bautitz I R, Nogueira R F P. Photodegradation of lincomycin and diazepam in sewage treatment plant effluent by photo-Fenton process[J]. Catalysis Today, 2010,151(1/2):94-99.
[25] 雷雨洋,李方方,欧阳洁,等.浙江地区抗生素残留的环境分布特征及来源分析[J].化学进展, 2021,33(8):1414-1425. Lei Y Y, Li F F, Ouyang J, et al. Environmental distribution characteristics and source analysis of antibiotic residues in Zhejiang Province[J]. Progress in Chemistry, 2021,33(8):1414-1425.
[26] 林洁,曹建明,蔡欣欣,等.超高效液相色谱三重四极杆质谱法快速测定蜂蜜中12种大环内酯和林可酰胺类药物残留[J].中国卫生检验杂志, 2010,20(5):959-962. Lin J, Cao J M, Cai X X, et al. Rapid determination of 12 macrolide and lincomycin antibiotic residues in honey by ultra-high performance liquid chromatography-triple quadrupole mass spectrometry[J]. Chinese Journal of Health Laboratory Technology, 2010,20(5):959-962.
[27] Yang S, Cha J, Carlson K. Quantitative determination of trace concentrations of tetracycline and sulfonamide antibiotics in surface water using solid-phase extraction and liquid chromatography/ion trap tandem mass spectrometry[J]. Rapid Communications in Mass Spectrometry Rcm, 2010,18(18):2131-2145.
[28] Song C, Liu H Y, Guo S, et al. Photolysis mechanisms of tetracycline under UV irradiation in simulated aquatic environment surrounding limestone[J]. Chemosphere, 2020,244:125582.
[29] Yang Y, Xu R, Feng Q, et al. Adsorption characteristics of three quinolone antibiotics on sediment from drinking water source of Luoma Lake[J]. Environmental Pollution&Control, 2020,42(6):717-722.
[30] Sun F, Wu D, Chua F D, et al. Free nitrous acid (FNA) induced transformation of sulfamethoxazole in the enriched nitrifying culture[J]. Water Research, 2019,149:432-439.
[31] Dines G P. The macrolide antibiontic renaissance[J]. Br. J. Pharmacol., 2017,174(18):2967-2983.
[32] Guo J, Selby K, Boxall A B. Comparing the sensitivity of chlorophytes, cyanobacteria, and diatoms to major-use antibiotics[J]. Environ. Toxicol. Chem., 2016,35(10):2587-2596.
[33] Baran W, Adamek E, Ziemiańska J, et al. Effects of the presence of sulfonamides in the environment and their influence on human health[J]. Journal of Hazardous Materials, 2011,196:1-15.
[34] Baran W, Adamek E, Ziemianska J, et al. Effects of the presence of sulfonamides in the environment and their influence on human health[J]. 2011,196:1-15.
[35] Zhang R, Tang J, Li J, et al. Antibiotics in the offshore waters of the Bohai Sea and the Yellow Sea in China:Occurrence, distribution and ecological risks[J]. Environmental Pollution, 2013,174:71-77.
[36] 方龙飞,魏群山,王元宏,等.上海黄浦江上游典型抗生素来源及分布污染特征研究[J].环境污染与防治, 2017,(3):303. Fang L F, Wei Q S, et al. Study on the sources and distribution pollution characteristics of typical antibiotics in the upstream of the Huangpu River in Shanghai[J]. Environmental Pollution and Control, 2017,(3):303.
[37] Guo F, Wang Y, Peng J, et al. Occurrence, distribution, and risk assessment of antibiotics in the aquatic environment of the karst plateau wetland of Yangtze river basin, southwestern China[J]. Int. J. Environ. Res. Public Health, 2022,19(12):7211.
[38] Chen H, Li X, Zhu S. Occurrence and distribution of selected pharmaceuticals and personal care products in aquatic environments:A comparative study of regions in China with different urbanization levels[J]. Environmental Science and Pollution Research, 2012,19(6):2381-2389.
[39] Mehrtens A, Licha T, Burke V. Occurrence, effects and behaviour of the antibiotic lincomycin in the agricultural and aquatic environment-A review[J]. Science of the Total Environment, 2021,778:146306.
[40] Zhang X, Wang J, Duan B, et al. Degradation of sulfamethoxazole in water by a combined system of ultrasound/PW12/KI/H2O2[J]. Separation and Purification Technology, 2021,270:118790.
[41] Li X, Jiang X J, Qi D X, et al. Effects of ethanamizuril, sulfachlorpyridazine or their combination on cecum microbial community and metabolomics in chickens infected with Eimeria tenella[J]. Microbial Pathogenesis, 2022,173:105823.
[42] Li Y, Wang J, Lin C, et al. Riverine antibiotic occurrence and potential ecological risks in a low-urbanized and rural basin of the middle Yangtze River:Socioeconomic, land use, and seasonal effects[J]. Environmental Research, 2023,228:115827.
[43] 封丽,程艳茹,封雷,等.三峡库区主要水域典型抗生素分布及生态风险评估[J].环境科学, 2017,30(7):1031-1040. Feng L, Cheng Y R, Feng L, et al. Distribution of typical antibiotics and ecological risk assessment in the main water bodies of the Three Gorges Reservoir Area[J]. Environmental Science, 2017,30(7):1031-1040.
[44] Bialk-Bielinska A, Stolte S, Aming J, et al. Ecotoxicity evaluation of selected sulfonamides[J]. Chemosphere, 2011,85(6):928-933.
[45] Pro J, Ortiz J A, Boleas S, et al. Effect assessment of antimicrobial pharmaceuticals on the aquatic plant Lemna minor[J]. Bulletin of Environmental Contamination and Toxicology, 2003,70(2):290-295.
[46] Li M H. Comparative toxicities of 10 widely used biocides in three freshwater invertebrate species[J]. Chemistry and Ecology, 2019, 35(5):472-482.
[47] 王林芳.汾河流域典型抗生素污染特征及归趋研究[D].太原:山西大学, 2021. Wang L F. Study on the pollution characteristics and fate of typical antibiotics in the Fen River Basin[D]. Taiyuan:Shanxi University, 2021.
[48] Wu S, Qi L, Ren Y, et al. 1,2,4-triazole-3-thione Schiff bases compounds:Crystal structure, hirshfeld surface analysis, DFT studies and biological evaluation[J]. Journal of Molecular Structure, 2020, 1219:128591.
[49] Ebert I, Bachmann J, Kühnen U, et al. Toxicity of the fluoroquinolone antibiotics enrofloxacin and ciprofloxacin to photoautotrophic aquatic organisms[J]. Environ Toxicol Chem, 2011,30(12):2786-92.
[50] Pomati F, Netting A G, Calamari D, et al. Effects of erythromycin, tetracycline and ibuprofen on the growth of Synechocystis sp. and Lemna minor[J]. Aquatic Toxicology, 2004,67(4):387-396.
[51] Robinson A A, Belden J B, Lydy M J. Toxicity of fluoroquinolone antibiotics to aquatic organisms[J]. Environmental Toxicology and Chemistry, 2005,24(2):423-430.
[52] Montanes M T, Garcia-Gabaldon M, Roca-Perez L, et al. Analysis of norfloxacin ecotoxicity and the relation with its degradation by means of electrochemical oxidation using different anodes[J]. Ecotoxicology and Environmental Safety, 2020,188:109923.
[53] de Orte M R, Carballeira C, Viana I G, et al. Assessing the toxicity of chemical compounds associated with marine land-based fish farms:The use of mini-scale microalgal toxicity tests[J]. Chemistry and Ecology, 2013,29(6):554-563.
[54] Backhaus T, Faust M. Predictive environmental risk assessment of chemical mixtures:a conceptual framework[J]. Environmental Science&Technology, 2012,46(5):2564-2573.
[55] Backhaus T, Faust M. Predictive environmental risk assessment of chemical mixtures:a conceptual framework[J]. Environ. Sci. Technol., 2012,46(5):2564-73.