Journal of Guangxi Normal University(Natural Science Edition) ›› 2025, Vol. 43 ›› Issue (4): 165-174.doi: 10.16088/j.issn.1001-6600.2024090801

• Ecology and Environmental Science Research • Previous Articles     Next Articles

Effect of Montmorillonite-Humic Acid Composite Particles on Photolysis of Tetracycline

NIE Qinping, WANG Zirui, HOU Xiaomin, WU Qingfeng*   

  1. School of Physics and Optoelectronic Engineering, Yangtze University, Jingzhou Hubei 434023, China
  • Received:2024-09-08 Revised:2024-11-14 Online:2025-07-05 Published:2025-07-14

Abstract: Suspended particulate matter (SPM) is an important component of natural water body and can significantly influence the photolytic behavior of water pollutants. A comprehensive understanding about the photochemical behavior of water pollutants in natural waters requires consideration of the presence of SPM. In this study, montmorillonite-humic acids (MMT-HAs) composite particle was prepared to simulate SPM in natural waters, and their effects on the photolysis of tetracycline (TC) were investigated. The results demonstrated that the presence of MMT-HAs composite particle in water significantly enhanced the photolysis of TC, with the photolytic kinetics following a pseudo-first-order model. Electron spin resonance spectra and free radical quenching experiments indicated that the photoactive components (MMT and humic acids) in the composite particle induced the generation of reactive oxygen species under light exposure, contributing to the enhanced photolysis of TC. Comparative analysis of the photolysis of TC in the MMT and MMT-HAs particle systems and adsorption experiments further revealed that the promoted photolysis of TC was also related to the interfacial interaction between MMT-HAs composite particles and TC molecules. The formation of surface complex between amino groups of TC and the negatively charged sites on MMT surface facilitated light absorption or electron transfer, thereby accelerating the photolysis of TC. The promotion of TC photolysis by MMT-HAs composite particles was the result of the combined action of these two mechanisms. Photoproduct analysis indicated that the hydroxyl radical addition to the aromatic ring of TC, as well as demethylation, deamination and dehydration in the side chains were the main degradation pathways of TC in the composite particle systems. The findings can provide valuable insights into the photolytic behavior of water pollutants in natural waters.

Key words: suspended particles, montmorillonite, humic acid, tetracycline, photolysis, free radical, interfacial adsorption

CLC Number:  TQ424;X52
[1] WILKINSON J L, BOXALL A B A, KOLPIN D W, et al. Pharmaceutical pollution of the world's rivers[J]. Proceedings of the National Academy of Sciences of the United States of America, 2022, 119(8): e2113947119. DOI: 10.1073/pnas.2113947119.
[2] BAVUMIRAGIRA J P, GE J N, YIN H L. Fate and transport of pharmaceuticals in water systems: a processes review[J]. Science of the Total Environment, 2022, 823: 153635. DOI: 10.1016/j.scitotenv.2022.153635.
[3] ROUT P R, ZHANG T C, BHUNIA P, et al. Treatment technologies for emerging contaminants in wastewater treatment plants: a review[J]. Science of the Total Environment, 2021, 753: 141990. DOI: 10.1016/j.scitotenv.2020.141990.
[4] ZHANG Q Q, YING G G, PAN C G, et al. Comprehensive evaluation of antibiotics emission and fate in the river basins of China: source analysis, multimedia modeling, and linkage to bacterial resistance[J]. Environmental Science & Technology, 2015,49(11): 6772-6782. DOI: 10.1021/acs.est.5b00729.
[5] HEBERER T. Tracking persistent pharmaceutical residues from municipal sewage to drinking water[J]. Journal of Hydrology, 2002, 266(3/4): 175-189. DOI: 10.1016/S0022-1694(02)00165-8.
[6] WEI R C, GE F, HUANG S Y, et al. Occurrence of veterinary antibiotics in animal wastewater and surface water around farms in Jiangsu Province, China[J]. Chemosphere, 2011, 82(10): 1408-1414. DOI: 10.1016/j.chemosphere.2010.11.067.
[7] SUN J T, ZENG Q T, TSANG D C W, et al. Antibiotics in the agricultural soils from the Yangtze River Delta, China[J]. Chemosphere, 2017, 189: 301-308. DOI: 10.1016/j.chemosphere.2017.09.040.
[8] SHI H, YANG Y, LIU M, et al. Occurrence and distribution of antibiotics in the surface sediments of the Yangtze Estuary and nearby coastal areas[J]. Marine Pollution Bulletin, 2014, 83(1): 317-323. DOI: 10.1016/j.marpolbul.2014.04.034.
[9] WANG X H, LIN A Y C. Is the phototransformation of pharmaceuticals a natural purification process that decreases ecological and human health risks?[J]. Environmental Pollution, 2014, 186: 203-215. DOI: 10.1016/j.envpol.2013.12.007.
[10] BHAT A P, POMERANTZ W C K, ARNOLD W A. Wavelength-dependent UV-LED photolysis of fluorinated pesticides and pharmaceuticals[J]. Environmental Science & Technology, 2023, 57(13): 5327-5336. DOI: 10.1021/acs.est.3c00627.
[11] CHOWDHURY P, SARATHY S R, DAS S, et al. Direct UV photolysis of pharmaceutical compounds: determination of pH-dependent quantum yield and full-scale performance[J]. Chemical Engineering Journal, 2020, 380: 122460. DOI: 10.1016/j.cej.2019.122460.
[12] SCISCENKO I, ARQUES A, VARGA Z, et al. Significant role of iron on the fate and photodegradation of enrofloxacin[J]. Chemosphere, 2021, 270: 129791. DOI: 10.1016/j.chemosphere.2021.129791.
[13] BAI Y, ZHOU Y L, CHE X W, et al. Indirect photodegradation of sulfadiazine in the presence of DOM: effects of DOM components and main seawater constituents[J]. Environmental Pollution, 2021, 268, Part B: 115689. DOI: 10.1016/j.envpol.2020.115689.
[14] WEI L X, LI H X, LU J F. Algae-induced photodegradation of antibiotics: a review[J]. Environmental Pollution, 2021, 272: 115589. DOI: 10.1016/j.envpol.2020.115589.
[15] 黄宏,李圆杏,杨红伟.水环境中抗生素的光降解研究进展[J].环境化学,2013,32(7):1335-1341. DOI: 10.7524/j.issn.0254-6108.2013.07.029.
[16] WALCH H, VON DER KAMMER F, HOFMANN T. Freshwater suspended particulate matter-key components and processes in floc formation and dynamics[J]. Water Research, 2022, 220: 118655. DOI: 10.1016/j.watres.2022.118655.
[17] 胡学香,陈勇,聂玉伦,等.水中四环素类化合物在不同光源下的光降解[J].环境工程学报,2012,6(8):2465-2469.
[18] NIU J F, LI Y, WANG W L. Light-source-dependent role of nitrate and humic acid in tetracycline photolysis: kinetics and mechanism[J]. Chemosphere, 2013, 92(11): 1423-1429. DOI: 10.1016/j.chemosphere.2013.03.049.
[19] GOURNIS D, KARAKASSIDES M A, PETRIDIS D. Formation of hydroxyl radicals catalyzed by clay surfaces[J]. Physics and Chemistry of Minerals, 2002, 29(2): 155-158. DOI: 10.1007/s002690100215.
[20] 孙昊婉,张立秋,封莉.光诱导腐殖酸产生自由基对天然水中雌二醇光降解效能的影响[J].环境工程学报,2017,11(11):5794-5798. DOI: 10.12030/j.cjee.201702118.
[21] WANG M J, SHI H H, SHAO S, et al. Montmorillonite promoted photodegradation of amlodipine in natural water via formation of surface complexes[J]. Chemosphere, 2022, 286(1): 131641. DOI: 10.1016/j.chemosphere.2021.131641.
[22] XU L P, LI H, MITCH W A, et al. Enhanced phototransformation of tetracycline at smectite clay surfaces under simulated sunlight via a Lewis-base catalyzed alkalization mechanism[J]. Environmental Science & Technology, 2019, 53(2): 710-718. DOI: 10.1021/acs.est.8b06068.
[23] LI S, HU J Y. Photolytic and photocatalytic degradation of tetracycline: effect of humic acid on degradation kinetics and mechanisms[J]. Journal of Hazardous Materials, 2016, 318: 134-144. DOI: 10.1016/j.jhazmat.2016.05.100.
[24] ZHU X D, WANG Y J, SUN R J, et al. Photocatalytic degradation of tetracycline in aqueous solution by nanosized TiO2[J]. Chemosphere, 2013, 92(8): 925-932. DOI: 10.1016/j.chemosphere.2013.02.066.
[25] BUXTON G V, GREENSTOCK C L, HELMAN W P, et al. Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (·OH/·O-) in aqueous solution[J]. Journal of Physical and Chemical Reference Data, 1988, 17(2): 513-886. DOI: 10.1063/1.555805.
[26] JIAO S J, ZHENG S R, YIN D Q, et al. Aqueous photolysis of tetracycline and toxicity of photolytic products to luminescent bacteria[J]. Chemosphere, 2008, 73(3): 377-382. DOI: 10.1016/j.chemosphere.2008.05.042.
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