浅层地下水中磺胺嘧啶与胡敏酸相互作用及相态间分布特征

doi:10.13745/j.esf.sf.2021.2.20

摘要/Abstract

摘要：

研究抗生素在浅层地下水中不同相态间的分布特征,对于了解抗生素的行为特征及评估其危害具有重要的意义。本文利用三维荧光淬灭法研究了胡敏酸(humic acid, HA)对磺胺嘧啶(sulfadiazine, SD)在地下水中不同相态间分布规律的影响及相互作用,探讨了HA浓度、pH值、温度对SD在不同相态间分布的影响,对淬灭过程进行拟合并计算了分配系数、淬灭参数以及热力学参数。结果表明:地下水中SD浓度(0.5 mg/L)较低时或者HA浓度增加(0~20 mg/L)时,HA可显著促进悬浮相中SD比例的增加;SD对HA的淬灭机理为形成复合物的单一静态淬灭,结合位点数均约为1,荧光淬灭常数K_sv为5.271×10³ L/mol,淬灭速率常数K_q为5.271×10¹¹ L/(mol·s),属于自发的放热过程;体系处于低温(15 ℃)、弱碱性(8~10)pH值环境时,SD对HA的淬灭作用最强,HA对SD进入悬浮相的促进作用最明显。

关键词: 三维荧光法, 胡敏酸, 磺胺嘧啶, 相互作用, 相态间分布

Abstract:

It is important for exploring the behavioral characteristics of antibiotics and assessing their hazards by studying the distribution characteristics of antibiotics in shallow groundwater. In this paper, the interaction of sulfadiazine (SD) with humic acid (HA) and the effect of HA on the phase distribution of SD in shallow groundwater were studied by three-dimensional fluorescence quenching method. The effects of HA concentration, pH and temperature on SD in different phases were discussed, and the distribution coefficient as well as quenching and thermodynamic parameters for the quenching process were calculated. The results showed that both low SD (0.5 mg/L) and elevated HA (0-20 mg/L) can significantly increase SD partition in the suspension phase. The mechanism of HA fluorescence quenching by SD was to form HA·SD complex via a single static process. The number of binding site was 1; the quenching constant K_sv was 5.271×10³ L/mol; and the quenching rate constant K_q was 5.271×10 ¹¹ L/(mol·s). It showed the HA-SD interaction was a spontaneous exothermic process. In a low-temperature (15 ℃), neutral or weakly alkaline (pH 8-10) environment, antibiotics had the strongest quenching effect on HA, and, accordingly, HA had the most obvious promoting effect on SD entering the suspension phase.

Key words: three-dimensional fluorescence method, humic acid, sulfadiazine, interaction, distribution between phases

中图分类号:

X523

段磊, 杨胜科, 王文科. 浅层地下水中磺胺嘧啶与胡敏酸相互作用及相态间分布特征[J]. 地学前缘, 2021, 28(5): 104-113.

DUAN Lei, YANG Shengke, WANG Wenke. Effect of humic acid on the phase distribution of sulfadiazine in shallow groundwater[J]. Earth Science Frontiers, 2021, 28(5): 104-113.

图/表 12

图1 悬浮物粒径分布

Fig.1 Particle size distribution in suspended matter

图2 HA的三维荧光图 a、b、c、d图分别代表HA浓度为2、4、6、10 mg/L的情况。

Fig.2 Three-dimensional fluorescence image of HA

图3 SD在相态间的平衡浓度分布及分配系数Kd随SD初始浓度变化

Fig.3 Sulfadiazine partition between phases at equilibrium (left) and SD phase distribution coefficient Kd(right) as a function of SD initial concentration

图4 HA对SD在相态间分布的影响

Fig.4 Effect of HA on SD phase distribution

图5 HA与SD在悬浮相中分布示意图

Fig.5 Humic acid and SD distributions in the suspension phase

图6 25 ℃和pH 7条件下不同浓度SD对HA荧光淬灭图图中SD的单位为mg/L。

Fig.6 Humic acid fluorescence quenching curves for varying SD concentrations at 25 ℃ and pH 7

图7 25 ℃下SD荧光淬灭的Stern-Volmer曲线

Fig.7 Stern-Volmer curve of HA fluorescence quenching by SD at 25 ℃

图8 不同温度条件下SD对HA荧光淬灭的Stern-Volmer曲线

Fig.8 Stern-Volmer curve of HA fluorescence quenching by SD for different temperatures

图9 不同pH值条件下SD对HA荧光淬灭作用

Fig.9 Humic acid fluorescence quenching by SD at varying pH

图10 不同pH值条件下SD对HA荧光淬灭的Stern-Volmer曲线

Fig.10 Stern-Volmer curve of HA fluorescence quenching by SD for varying pH

表1 不同温度下SD-HA作用的热力学参数

Table 1 Thermodynamic parameters for SD-HA interaction at different temperatures

抗生素	pH 值	K_sv/ (10³L·mol^-1)	K_q/ (10¹¹L·mol^-1·s^-1)	K_b/ (10³L·mol^-1)	n
SD	4	3.894	3.894	3.724	1.34
	8	4.043	4.043	4.015	0.69
	10	3.946	3.946	3.824	0.81

图11 SD、HA、HA-SD傅里叶红外光谱图

Fig.11 Fourier infrared spectrum of SD, HA or HA-SD

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