聚苯乙烯微塑料对水中汞离子的吸附研究

doi:10.16258/j.cnki.1674-5906.2022.10.013

生态环境学报 ›› 2022, Vol. 31 ›› Issue (10): 2048-2057.DOI: 10.16258/j.cnki.1674-5906.2022.10.013

聚苯乙烯微塑料对水中汞离子的吸附研究

雷雅杰, 李雪, 常春艳, 毛雪飞^*()

中国农业科学院农业质量标准与检测技术研究所/农业农村部农产品质量安全重点实验室，北京 100081

收稿日期:2022-05-22 出版日期:2022-10-18 发布日期:2022-12-09
通讯作者: ^*毛雪飞（1983年生），男，研究员，博士，研究方向为农产品与环境质量安全。E-mail: mxf08@163.com, maoxuefei@caas.cn
作者简介:雷雅杰（1997年生），男，硕士研究生，研究方向为农产品质量与安全。
基金资助:
西藏自治区科技计划项目(XZ202001ZY0048N);中央级公益性科研院所基本科研业务费(1610072021003);国家重点研发计划项目(2021YFD2000202)

Adsorption of Mercury Ions in Water by Polystyrene Microplastics

LEI Yajie, LI Xue, CHANG Chunyan, MAO Xuefei^*()

Institute of Quality Standard and Testing Technology for Agro-Products, Chinese Academy of Agricultural Sciences/Key Laboratory of Agrifood Safety and Quality, Ministry of Agriculture and Rural Affairs, Beijing 100081, P. R. China

Received:2022-05-22 Online:2022-10-18 Published:2022-12-09

摘要/Abstract

摘要：

微塑料（MPs）和重金属汞（Hg）之间的相互作用会对水环境及水生生物产生潜在危害，目前尚缺乏水环境中MPs对Hg吸附行为的系统研究。利用直接进样测汞仪、场发射扫描电镜-能谱仪和傅里叶变换红外光谱仪等手段，研究不同吸附时间、溶液pH、离子强度、PS-MPs粒径、环境温度等条件下PS-MPs对Hg²⁺的吸附行为以及相关的物化参数，探究环境中广泛存在的聚苯乙烯微塑料（PS-MPs）与水环境中Hg²⁺之间的相互作用，评价PS-MPs和Hg的环境行为。结果表明，平均粒径为60 μm的PS-MPs能在数分钟内快速吸附Hg²⁺，在4 h内达到吸附平衡；PS-MPs对Hg²⁺的吸附动力学符合准二级动力学模型，吸附等温线遵循Freundlich模型。其对Hg²⁺的最大吸附量为291.03 ng·mg^-1，在此范围内溶液中Hg²⁺含量越高，PS-MPs的吸附量越大。吸附过程存在多个吸附阶段且以非线性多分子层吸附机制为主，结合能谱和红外光谱结果证明了PS-MPs与Hg²⁺的吸附过程主要包括静电、范德华力和化学络合吸附作用。另外，该研究还发现当溶液pH为7.0时，PS-MPs对100 ng·g^-1 Hg²⁺的平衡吸附量最大，约为41.51 ng·mg^-1；温度越高，粒径更小的PS-MPs对Hg²⁺的平衡吸附量大；溶液中离子强度越高，Hg²⁺吸附量降低。该论文为实际环境中PS-MPs和重金属Hg的混合污染治理提供了一定的理论参考，今后还需进一步研究PS-MPs和Hg结合对水生生物的生物效应。

关键词: 聚苯乙烯微塑料, 汞离子, 吸附作用, 动力学, 等温线

Abstract:

The interaction between microplastics (MPs) and mercury (Hg) can cause potential risks to water environment and aquatic organisms. However, to the best of our knowledge, the systematic adsorption behavior of MPs and Hg in water environment has not been reported so far. The purpose of the article is to explore the interaction between polystyrene microplastics (PS-MPs) and Hg²⁺ widely existing in water environment as well as to evaluate their mutual behavior. Herein, the adsorption behavior of PS-MPs with Hg²⁺ and their related physicochemical properties were studied under different experimental conditions, including adsorption time, pH values, ionic levels, PS-MPs particle sizes, and environmental temperatures, using solid sampling Hg analyzer, scanning electron microscope, X-ray energy dispersive spectrometer (EDS) and Fourier transform infrared spectrometer. Results show that PS-MPs (average 60 μm particle size) can rapidly adsorb Hg²⁺in a few minutes and then reach the adsorption equilibrium within 4 h; the adsorption kinetics of Hg²⁺ by PS-MPs conform the pseudo-second order kinetics, while the adsorption isotherm follows the Freundlich model. With the increase in Hg²⁺ content in solution, the Hg²⁺ adsorption capacity of PS-MPs becomes higher, with the maximum adsorption of 291.03 ng·mg^-1. The adsorption behavior of PS-MPs and Hg²⁺ is mainly controlled by the nonlinear multi-molecular layer absorption mechanism, consisting of multiple stages caused by the mutual role of static electricity, van der Waals force and chemical complexation adsorption, which has been proved by the results of energy spectroscopy and infrared spectroscopy. In addition, the study also found that when the pH value was 7.0, the equilibrium adsorption capacity of PS-MPs for 100 ng·g^-1 Hg²⁺ reached maximum (41.51 ng·mg^-1). The higher the temperature, the greater the equilibrium adsorption capacity of Hg²⁺ by PS-MPs with smaller particle size. With the increasing ionic level in the solution, the adsorption capacity of Hg²⁺ was reduced. This work is theoretically helpful for the further investigation of the mixed pollution of PS-MPs and mercury and their environmental remediation in the future and the biological effects between PS-MPs and Hg on aquatic organisms should be further studied.

Key words: polystyrene microplastics, mercury ion, adsorption, kinetics, isotherms

中图分类号:

X131.2

雷雅杰, 李雪, 常春艳, 毛雪飞. 聚苯乙烯微塑料对水中汞离子的吸附研究[J]. 生态环境学报, 2022, 31(10): 2048-2057.

LEI Yajie, LI Xue, CHANG Chunyan, MAO Xuefei. Adsorption of Mercury Ions in Water by Polystyrene Microplastics[J]. Ecology and Environment, 2022, 31(10): 2048-2057.

图/表 13

图1 不同N2相对压力下的吸附和解吸附曲线（a）和不同孔径下的孔容（b）

Figure 1 Adsorption and desorption curves under different N2 relative pressures (a) and pore volume under different pore diameters (b)

图2 PS-MPs的粒径分布图

Figure 2 Particle size distribution of PS-MPs

图3 不同pH下PS-MPs的Zeta电位

Figure 3 Zeta potentials of PS-MPs at different pH values

图4 不同粒径PS-MPs的扫描电镜图

Figure 4 SEM image of PS-MPs with different particle sizes

图5 PS-MPs吸附Hg2+前后红外光谱

Figure 5 Infrared spectra of PS-MPs before and after Hg2+ adsorption

图6 PS-MPs对Hg2+的吸附动力学

Figure 6 Adsorption kinetics of Hg2+ on PS-MPs

表1 PS-MPs吸附Hg2+的吸附动力学拟合参数

Table 1 Fitting parameters of adsorption kinetics of Hg2+ on PS-MPs

准一级动力学模型Pesudo-first order kinetic model				准二级动力学模型 Pseudo-second order kinetic mode
Q_e/(ng·mg^-1)	k₁/min^-1	R₁²		Q_e/(ng·mg^-1)	k₂/(g·ng^-1·min^-1)	R₂²
31.540	0.027	0.955		33.184	0.00117	0.967

图7 PS-MPs对Hg2+的吸附热力学

Figure 7 Adsorption thermodynamics of Hg2+ on PS-MPs

表2 PS-MPs吸附Hg2+的吸附等温线参数

Table 2 Adsorption isotherm parameters for the adsorption of Hg2+ by PS-MPs

Langmuir模型 Langmuir model				Freundlich模型 Freundlich model
Q_max/(ng·mg^-1)	K_L/(L·ng^-1)	R₁²		K_f/(mL³·g^-1)	n	R₂²
291.03	0.00115	0.945		496.80	0.0866	0.952

图8 PS-MPs在不同pH条件下对Hg2+的吸附不同字母（a、b、c、d、e）代表不同pH条件下之间吸附量的显著差异（P<0.05）

Figure 8 Adsorption of Hg2+ by PS-MPs under different pH values The different letters (a, b, c, d and e) are significantly different for adsorption levels among different pH values

图9 PS-MPs在不同离子强度条件下对Hg2+的吸附 “*”代表不同离子强度之间吸附量的显著差异（P<0.05）

Figure 9 Adsorption of Hg2+ by PS-MPs under different ionic levels between adsorption levels and different ionic levels “*” are significantly different (P<0.05)

图10 PS-MPs在不同温度情况下对Hg2+的吸附不同字母（a、b、c、d）代表不同温度下吸附量的显著差异（P<0.05）

Figure 10 Adsorption of Hg2+ by PS-MPs at different temperatures The different letters (a, b, c and d) are significantly different for adsorption levels among different temperatures

表3 PS-MPs吸附Hg2+前后的平均质量数和平均原子数

Table 3 Average mass number and average atom number before and after adsorption of Hg2+ by PS-MPs

元素 Elements	60 μm PS-MPs			400 nm PS-MPs			60 μm PS-MPs-Hg²⁺			400 nm PS-MPs-Hg²⁺
元素 Elements	平均质量数Weight	平均原子数Atomic	误差 Error	平均质量数 Weight	平均原子数 Atomic	误差 Error	平均质量数 Weight	平均原子数 Atomic	误差 Error	平均质量数 Weight	平均原子数 Atomic	误差 Error
C K	91.038%	93.299%	0.434%	93.586%	95.381%	0.470%	95.974%	97.627%	0.499%	95.807%	97.521%	0.490%
O K	8.688%	6.684%	0.495%	6.004%	4.594%	0.512%	3.028%	2.313%	0.478%	3.162%	2.416%	0.471%
Hg L	0.274%	0.017%	0.494%	0.410%	0.025%	0.727%	0.998%	0.061%	0.887%	1.031%	0.063%	0.830%

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聚苯乙烯微塑料对水中汞离子的吸附研究

Adsorption of Mercury Ions in Water by Polystyrene Microplastics

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