金霉素和土霉素对生物除磷中微生物EPS的影响

doi:10.3964/j.issn.1000-0593(2024)04-1191-10

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摘要：金霉素和土霉素在城市污水处理厂中检出率较高，通常以混合物的形式存在于污水中。微生物胞外聚合物（EPS）作为保护层抵御外界有害物质的侵害，在微生物生命活动中发挥着重要作用。目前，关于金霉素和土霉素对生物除磷中微生物EPS的影响较少。为探究金霉素和土霉素对生物除磷中微生物EPS的影响，采用直接均分射线法设计3种不同浓度配比（L1、L2和L3）混合物，研究了不同浓度金霉素、土霉素单独作用及其混合物对EPS中蛋白质和多糖的影响。采用三维荧光光谱（3D-EEM）和傅里叶变换红外光谱（FTIR）分析金霉素和土霉素对EPS组分及结构的影响。结果表明：随着浓度增加和反应时间的延长，生物除磷系统性能逐渐恶化，微生物EPS中蛋白质和多糖含量均呈现先上升后下降的趋势，且蛋白质含量均高于多糖。3D-EEM分析表明，随金霉素、土霉素及其混合物浓度增加，EPS中类蛋白质物质荧光强度均先增强后减弱，浓度较高时产生了类腐殖酸物质和类富里酸物质。金霉素与土霉素之间存在拮抗作用，使得混合物荧光物质的荧光强度均弱于单独作用，只有配比L3中未出现类腐殖酸物质和类富里酸物质。FTIR分析表明，金霉素、土霉素及其混合物对EPS中1 653 cm^-1酰胺Ⅰ谱带的CO伸缩振动、1 403 cm^-1酰胺Ⅱ谱带的CO对称拉伸、1 266 cm^-1的PO伸缩振动、1 100 cm^-1的糖类C—OH伸缩振动均产生影响。金霉素与土霉素存在拮抗作用引起各官能团存在差异性，1 004 cm^-1的P—OH伸缩振动只存在于土霉素、配比L2、配比L3；900 cm^-1的P—O伸缩振动只存在于金霉素、土霉素、配比L2、配比L3；770 cm^-1的氨基酸COO变角振动只有金霉素中不存在。该研究将为科学评估金霉素和土霉素及其混合污染物对生物除磷中微生物EPS影响机制提供理论依据。

关键词：金霉素；土霉素；胞外聚合物；生物除磷

Abstract：Chlortetracycline and oxytetracycline have high detection rates in wastewater treatment plants, usually coexisting in wastewater. Microbial extracellular polymeric substances (EPS) are the protective layers of the microbial cells against harmful substances, which play an important role in microbial life activities. Chlortetracycline and oxytetracycline may have a certain impact on microbial EPS. Nevertheless, there are few studies on the effects of chlortetracycline and oxytetracycline on microbial EPS during biological phosphorus removal. Three mixtures with different rates (L1, L2 and L3) were designed by direct equalization ray method to investigate the effects of chlortetracycline and oxytetracycline on microbial EPS. The effects of chlortetracycline and oxytetracycline and their mixtures on proteins and polysaccharides of EPS were studied. Three-dimensional fluorescence spectroscopy (3D-EEM) and Fourier transform infrared spectroscopy (FT-IR) was used to analyze the effects of chlortetracycline and oxytetracycline on the composition and structure of EPS. The results showed that, with the increase in concentration and the prolongation of reaction time, the performance of the biological phosphorus removal system gradually deteriorated. The contents of protein and polysaccharide of EPS increased first and then decreased, and the protein content was higher than that of polysaccharide. 3D-EEM analysis showed that, with the increase of chlortetracycline, oxytetracycline and their mixtures, the fluorescence intensity of protein-like substances of EPS first increased and then decreased, and humic and fulvic acid-like substances were produced when the concentration was higher. There was antagonism between chlortetracycline and oxytetracycline, so the fluorescence intensity of the mixture was weaker than that of the single action, and only the ratio L3 did not appear as a humic acid and fulvic acid substance. FTIR analysis showed that the CO stretching vibration of 1 653 cm^-1 amido Ⅰ band, the CO symmetric stretching of 1 403 cm^-1 amido Ⅱ band, the PO stretching vibration of 1 266 cm^-1 and the carbohydrate C—OH stretching vibration of 1 100 cm^-1 in EPS were affected by chlortetracycline, oxytetracycline and their mixtures. The antagonism between chlortetracycline and oxytetracycline causes differences in functional groups. The P—OH stretching vibration of 1004 cm^-1 only exists in oxytetracycline, ratio L2 and ratio L3, The P—O stretching vibration of 900 cm^-1 only exists in chlortetracycline, oxytetracycline, ratio L2 and ratio L3. It was absent for 770 cm^-1 amino acid COO variable angle vibration only in chlortetracycline. This study will provide a theoretical basis for the scientific evaluation of the mechanism of effects of chlortetracycline and oxytetracycline and their mixed pollutants on microbial EPS during biological phosphorus removal.

Key words：Chlortetracycline; Ooxytetracycline; Extracellular polymeric substance; Biological phosphorus removal

收稿日期: 2022-11-11 修订日期: 2023-07-23

中图分类号:

X703

基金资助: 安徽省高校优秀科研创新团队项目（2022AH010019），安徽省高校自然科学研究项目（2022AH050241, KJ2020A0466，KJ2021A0619），国家重点研发计划专项项目（2019YFC0408504），安徽建筑大学引进人才及博士启动基金项目（2019QDZ64，2019QDZ60）资助

通讯作者: 张华 E-mail: zhanghuapaper@163.com

作者简介: 陶传奇，1996年生，安徽建筑大学环境与能源工程学院硕士研究生 e-mail: 1545731537@qq.com

引用本文:

陶传奇，张华，黄健，奚姗姗，何春华，罗涛，王金花，张佳妹，马牧野. 金霉素和土霉素对生物除磷中微生物EPS的影响[J]. 光谱学与光谱分析, 2024, 44(04): 1191-1200.
TAO Chuan-qi, ZHANG Hua, HUANG Jian, XI Shan-shan, HE Chun-hua, LUO Tao, WANG Jin-hua, ZHANG Jia-mei, MA Mu-ye. Effects of Chlortetracycline and Oxytetracycline on Microbial EPS During Biological Phosphorus Removal. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2024, 44(04): 1191-1200.

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