环境化学2024,Vol.43Issue(12) :4238-4249.DOI:10.7524/j.issn.0254-6108.2023070201

溶解性有机质疏水性馏分的四环素络合机制

Complexation mechanism of tetracycline with fractionated hydrophobic components from dissolved organic matter

万洁婷 唐剑锋 杜妙柔 耿春女
环境化学2024,Vol.43Issue(12) :4238-4249.DOI:10.7524/j.issn.0254-6108.2023070201

溶解性有机质疏水性馏分的四环素络合机制

Complexation mechanism of tetracycline with fractionated hydrophobic components from dissolved organic matter

万洁婷 1唐剑锋 2杜妙柔 3耿春女3
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作者信息

  • 1. 上海应用技术大学生态技术与工程学院,上海,201418;中国科学院城市环境研究所宁波观测研究站,宁波,315830
  • 2. 中国科学院城市环境研究所宁波观测研究站,宁波,315830;中国科学院城市环境研究所城市环境与健康重点实验室,厦门,361021
  • 3. 上海应用技术大学生态技术与工程学院,上海,201418
  • 折叠

摘要

四环素属于两性化合物,含有显弱酸性的酚羟基和烯醇式羟基和显弱碱性的二甲氨基,因此溶解性有机质(DOM)的疏水性和亲水性,可能会影响它与四环素的络合能力.本文采用两种固相萃取柱对生活垃圾生物炭的DOM进行萃取分馏,得到以下4个馏分:疏水酸性组分(HOA)、疏水中性组分(HON)、疏水碱性组分(HOB)和亲水性组分(HIS).紫外光谱数据表明HON和HOB以疏水性组分为主,芳香化程度较高,它们的SUVA254、SUVA260分别为6.22-9.90、5.76-9.44 L·mg-1·m-1;而HIS则以亲水性组分为主,其SUVA254和SUVA260均为0.46 L·mg-1·m-1.DOM分馏增加了 HOB和HON的荧光值,显著降低了 HIS的荧光值,但是并没有影响微生物源腐殖质C1(80.7%-84.6%)和陆源类腐殖质C2(15.4%-19.3%)在各馏分中的分布.DOM和3个馏分(HON、HOB和HIS)的吸收光谱随着四环素浓度增大而升高,Stern-Volmer方程中的kq值(0.90×1012-3.89×1012 L·mol-1·s-1)远远大于最大散射碰撞猝灭常数(2x1010L·mol-1·s-1),因此属于静态猝灭.四环素与DOM的络合反应主要发生在微生物源腐殖质(C1)上,而陆源类腐殖质(C2)因为相对含量低而不呈现明显的络合作用.HON-C1与TC因结合位点少(n=1.22)而导致结合不稳定(lgKb=5.43),HON-C2与TC则因结合位点多(n=2.06)而引起结合很稳定(lgKb=8.47);DOM-C1、HOB-C1和HOB-C2的结合位点数和结合稳定性处于HON-C1和HON-C2之间.DOM因存在疏水性和亲水性组分对四环素的结合能力存在显著差异,从而影响了四环素在环境中的生态毒性和迁移转化能力.

Abstract

Tetracycline belongs to amphoteric compounds,containing phenolic hydroxyl groups and enol hydroxyl groups with a weak acidity as well as dimethylamino groups with a weak alkalinity.Therefore,the hydrophobicity and hydrophilicity of dissolved organic matter(DOM)may affect its chelating abilities with tetracycline.Two types of solid-phase extraction columns were used to extract and fractionate DOM from domestic waste biochar,resulting in following four fractions:hydrophobic acidic component(HOA),hydrophobic neutral component(HON),hydrophobic alkaline component(HOB),and hydrophilic component(HIS).The UV spectral data showed that HON and HOB were mainly of hydrophobic components,with a higher degree of aromatization,and their values of SUVA254 and SUVA260 are 6.22-9.90 Lmg-1·m-1 and 5.76-9.44 L mg-1·m-1.However,HIS was mainly composed of hydrophilic components,with SUVA254 and SUVA260 both being 0.46 L mg-1m-1.DOM fractionation increased the fluorescence values of HOB and HON while significantly reduced the fluorescence values of HIS,but did not affect the distribution of microbial humus Cl(80.7%-84.6%)and terrestrial humus C2(15.4%-19.3%)in each fraction.The absorption spectra of DOM and three fractions(HON,HOB,and HIS)increased with increasing tetracycline concentrations,and the kq values(0.90 × 1012-3.89 × 1012 L·mol-1·s-1)in the Stern Volmer Equation were much greater than the maximum scattering collision quenching constant(2 x 1010 L·mol-1·s-1);therefore,TC-DOM belonged to static quenching.On the contrary,the absorption spectra of DOM and three fractions(HON,HOB,and HIS)increased with increasing tetracycline concentrations,belonging to static quenching.The absorption peaks near 275 and 356 nm were linked to the characteristic peaks of tetracycline.The complexation reaction of tetracycline with DOM mainly occurred on microbial humus(Cl),while the complexation of terrestrial humus(C2)was not obvious due to its low relative content.In addition,HON-C1 complexation with TC was unstable(lgKb=5.43)due to limited binding sites(n=1.22),while HON-C2 complexation with TC was stable(lgKb=8.47)because of multiple binding sites(n=2.06).The number of binding sites and binding stabilities of DOM-C1,HOB-C1,and HOB-C2 were between HON-C1 and HON-C2.In summary,DOM has significant differences in the binding capacity of hydrophobic and hydrophilic components to tetracycline,which may affect the ecotoxicity,migration and transformation capacity of tetracycline in the environment.

关键词

生活垃圾生物炭/固相萃取与分馏/荧光猝灭/三维荧光光谱/同步光谱/四环素/结合位点方程/疏水性

Key words

domestic waste biochar/solid-phase extraction and fractionation/fluorescence quenching/three-dimensional fluorescence spectra/synchronous spectrum/tetracycline/binding site equation/hydrophobicity

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出版年

2024
环境化学
中国科学院生态环境研究中心

环境化学

CSTPCDCSCD北大核心
影响因子:1.049
ISSN:0254-6108
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