微塑料老化的人工干预及理化特性表征研究进展

doi:10.16085/j.issn.1000-6613.2022-0300

化工进展 ›› 2022, Vol. 41 ›› Issue (12): 6443-6453.DOI: 10.16085/j.issn.1000-6613.2022-0300

微塑料老化的人工干预及理化特性表征研究进展

陈国栋¹(), 刘海成¹^,²(), 孟无霜¹, 尤雨¹, 张皓¹, 曹梦茹¹

^1.苏州科技大学环境科学与工程学院，江苏苏州 215009
^2.河海大学浅水湖泊综合治理与资源开发教育部重点实验室，江苏南京 210098

收稿日期:2022-02-28 修回日期:2022-04-25 出版日期:2022-12-20 发布日期:2022-12-29
通讯作者: 刘海成
作者简介:陈国栋（1994—），男，硕士研究生，研究方向为微塑料环境污染与防治。E-mail：1372840158@qq.com。
基金资助:
中央高校基本科研业务费专项项目(2017B20514);苏州科技大学国家自然科学基金培育项目(XKZ2019007);江苏省研究生实践创新计划(SJCX20_1095)

Research progress on artificial intervention and characterization of physicochemical properties of microplastics aging

CHEN Guodong¹(), LIU Haicheng¹^,²(), MENG Wushuang¹, YOU Yu¹, ZHANG Hao¹, CAO Mengru¹

^1.College of Environmental Science and Engineering, Suzhou University of Science and Technology, Suzhou 215009, Jiangsu, China
^2.Key Laboratory of Integrated Regulation and Resource Development on Shallow Lakes, Ministry of Education, Hohai University, Nanjing 210098, Jiangsu, China

Received:2022-02-28 Revised:2022-04-25 Online:2022-12-20 Published:2022-12-29
Contact: LIU Haicheng

摘要/Abstract

摘要：

微塑料在环境中会经历自然老化的过程。由于存在老化发生缓慢和过程复杂等问题，自然老化不利于开展环境中微塑料的长期命运和风险评估研究。因此，研究人员在试验中已普遍采用人工干预技术加速微塑料的老化进程，但所用加速老化的方法类型和参数条件却存在差异。本文总结了现有微塑料老化研究中所采用的人工干预技术，并指出了各自的特点及适用性。在这些老化方法中，光辐射和高级氧化技术因操作简单、老化效果明显而应用尤为广泛。然后，从微观形貌、比表面积、表面官能团等多个方面阐述了老化过程引起的微塑料理化特性变化，并介绍了相应表征技术的应用。最后，针对未来的微塑料老化研究工作，提出了重视微塑料的原位环境老化研究、考虑多种老化途径或环境因素、考察添加剂或氧化副产物的释放问题以及制订微塑料老化的试验标准/协议等建议，以期为老化技术的发展和相关标准的制订提供支持。

关键词: 微塑料, 加速老化, 理化特性, 环境风险

Abstract:

Microplastics could undergo natural aging process in the environment. Due to the problems of slow aging and complex process, natural aging is not conducive to the research on long-term fate and risk assessment of microplastics in the environment. Therefore, the researchers used artificial intervention techniques to accelerate the aging process of microplastics in the experiment, but the method types and parameter conditions used to accelerate aging are different. This paper summarizes the artificial intervention techniques used in the existing microplastics aging research, and pointed out their characteristics and applicability. Among these aging methods, the optical radiation and advanced oxidation processes are widely used because of simple operation and obvious aging effect. Then, the changes in physicochemical properties of microplastics caused by aging process are described from the aspects of micro-morphology, specific surface area and surface functional groups, and introduced the application of corresponding characterization techniques. Finally, for the future research work of microplastics aging, some suggestions are proposed to provide support for aging technology development and relevant standards formulation, such as emphasizing the in situ environmental aging research of microplastics, considering various aging ways or environmental factors, investigating the release of additives or oxidation by-products, and formulating the standard / protocol of microplastics aging.

Key words: microplastics, accelerated aging, physicochemical properties, environmental risk

中图分类号:

X505

陈国栋, 刘海成, 孟无霜, 尤雨, 张皓, 曹梦茹. 微塑料老化的人工干预及理化特性表征研究进展[J]. 化工进展, 2022, 41(12): 6443-6453.

CHEN Guodong, LIU Haicheng, MENG Wushuang, YOU Yu, ZHANG Hao, CAO Mengru. Research progress on artificial intervention and characterization of physicochemical properties of microplastics aging[J]. Chemical Industry and Engineering Progress, 2022, 41(12): 6443-6453.

图/表 3

表1 微塑料的加速老化方法

类别	方法	参数					文献
类别	方法	微塑料	粒径	时间	介质	其他	文献
光辐射	UV-A 340nm	PS	0.1µm	90d	空气、纯水和模拟海水	25℃	［13］
	UV-B 313nm	PVC	50～100µm	25d	空气	50W/m²	［14］
	UV-C 254nm	PVC	D₅₀=139µm	60d	模拟海水	功率20W	［15］
	氙灯	PE	75～150µm	10d	空气	85℃、734W/m²	［16］
	汞灯365nm	PP	100～150µm	20d	超纯水、河口水或海水	25℃、100W/m²	［17］
	金属卤化物灯	PA6.6	4mm和100µm	77d	海水、空气	＜30℃、照度12200lx	［18］
高级氧化	热活化K₂S₂O₈	PP	<180µm	40d	100mL纯水中加入2.5g K₂S₂O₈	70℃	［19］
	Fenton	PS	—	7d	Fenton试剂、1.5%H₂O₂溶液	25℃±2℃、pH=4.0、振荡	［20］
	光Fenton	PS	50.4µm±11.9µm	5d	Fenton试剂	30℃、pH=3.0、10W/m²	［21］
	光催化	PP	3～5mm，厚约1mm	4h	纳米TiO₂包覆	60℃、湿度70%、1200W/m²	［22］
	O₃	色母粒	＜500µm	6h	浓度0.21mg/min、流速30mL/min	25℃	［23］
	放电等离子体	PVC	40～320µm	1h	干燥空气	空气流速1.0L/min、电压18kV、频率50Hz	［24］
高温热解		PS	平均1µm	90d	空气、纯水和模拟海水	75℃、pH=7.0	［25］
		PP颗粒	直径约2mm，长度4～5mm	20min	空气、N₂；气流200mL/min、气压0.1MPa	管式炉150℃、250℃、450℃和700℃	［26］
微生物降解	真菌	HDPE	＜200µm	28d	液体培养基	从蜡螟幼虫的肠道内容物分离，培养筛选微生物	［27］
高能辐射	γ射线	HDPE	90～106µm	—	—	1.17MeV，⁶⁰Co源	［28］
机械磨损		PP	＜5mm	5d	砂、纯水混合物	25℃、黑暗条件、摇床250r/min	［29］
环境因素		PA、PET、PS、PVC	150～550µm	90d	海水、沙子、土壤和空气	25℃、UV-A 340nm、功率20W	［30］

表2 微塑料加速老化的方法比较

类别	老化方法	控制参数	特点	适用性
光辐射	紫外灯、氙灯、汞灯等	辐照时间和强度、环境介质	老化周期较短，无须分离	较强
高级氧化	热活化K₂S₂O₈、光Fenton、O₃等	氧化剂种类和剂量	老化周期短，但氧化剂消耗量大，分离复杂	良好
高温热解	升温	温度、湿度	操作简单	良好
微生物降解	细菌、真菌等	菌属、培养条件	微生物需要分离和富集培养，老化周期较长	一般
高能辐射	γ射线	辐照剂量和时间	反应迅速，老化周期短	一般
机械磨损	沙子、恒温振荡器	沙子粒径、振荡速度	引起物理老化，分离较简单	良好

表3 几种常见微塑料的CI值计算方法

微塑料类型	计算方法	参考文献
PE	$C I = A b s 1613 c m - 1 A b s 2849 c m - 1$	［65］
	$C I = A b s 1654 ~ 1787 c m - 1 A b s 1403 ~ 1483 c m - 1$	［16］
	$C I = A b s 1710 c m - 1 A b s 2915 c m - 1$	［66］
	$C I = A b s 1712 c m - 1 A b s 1375 c m - 1$	［56］
PP	$C I = A b s 1712 c m - 1 A b s 1377 c m - 1$	［67］
	$C I = A b s 1715 c m - 1 A b s 974 c m - 1$	［17］
PS	$C I = A b s 1726 c m - 1 A b s 1452 c m - 1$	［68］
	$C I = A b s 1715 c m - 1 A b s 2851 c m - 1$	［69］

表3 几种常见微塑料的CI值计算方法

微塑料类型	计算方法	参考文献
PE	$C I = A b s 1613 c m - 1 A b s 2849 c m - 1$	［65］
	$C I = A b s 1654 ~ 1787 c m - 1 A b s 1403 ~ 1483 c m - 1$	［16］
	$C I = A b s 1710 c m - 1 A b s 2915 c m - 1$	［66］
	$C I = A b s 1712 c m - 1 A b s 1375 c m - 1$	［56］
PP	$C I = A b s 1712 c m - 1 A b s 1377 c m - 1$	［67］
	$C I = A b s 1715 c m - 1 A b s 974 c m - 1$	［17］
PS	$C I = A b s 1726 c m - 1 A b s 1452 c m - 1$	［68］
	$C I = A b s 1715 c m - 1 A b s 2851 c m - 1$	［69］

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微塑料老化的人工干预及理化特性表征研究进展

Research progress on artificial intervention and characterization of physicochemical properties of microplastics aging

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