土壤和植物中微塑料研究现状分析及检测方法研究进展

doi:10.13745/j.esf.sf.2023.11.51

摘要/Abstract

摘要：

微塑料(MPs)是指尺寸上限为5 mm的聚合物。作为一种新兴污染物,MPs广泛存在于海洋、陆地等不同环境中。研究发现,陆生环境是MPs一个重要的“汇”,其MPs的含量是海洋环境的4~23倍,MPs不仅影响土壤环境,还能够进入植物组织,并通过食物链等途径进入人体内,引发健康风险,成为迫切需要解决的环境污染问题。检测技术是研究环境污染物不可或缺的一个手段,关于陆生生态系统的研究刚起步,MPs检测技术还未发展成熟。目前,关于微塑料的检测主要分为前处理和分析检测:密度浮选、筛分过滤、萃取和消解等方法是前处理中常用的方法;定性定量检测以目检法、光谱法和质谱法为主,其中场发射扫描电镜(SEM)、激光共聚焦显微镜(CLSM)、拉曼光谱(Raman)、傅里叶变换红外光谱(FTIR)和热裂解-气相色谱/质谱法(Py-GC/MS)是最常用的仪器方法。而当面对复杂的环境样品时,往往需要结合多种方法进行分析。因此,本文通过文献整理,综述土壤及植物中MPs检测方法进展、不同检测技术的适用条件及优缺点,旨在为未来陆生生态系统MPs定性定量、MPs在植物中转移积累规律的研究提供科学参考。

关键词: 微塑料, 检测方法, 土壤, 植物, 新兴污染物

Abstract:

Microplastics (MPs) are tiny plastic particles less than 5 mm in length. As an emerging pollutant, MPs are widely found in the marine and terrestrial environments. It has been found that the terrestrial environment is an important sink for MPs, where the content of MPs is 4-23 times higher than the marine environment. Microplastics not only affect the soil environment, but also can enter plant tissues and the human body through food chain or other pathways, posing health risks and becoming an urgent environmental problem. Detection technology is an indispensable tool for the study of environmental pollutants, but research on terrestrial ecosystems is still in its infancy and detection technology for MPs is still developing. At present, the detection of microplastics is ususally done in two steps: sample pretreatment and sample analysis. Density flotation, sieving and filtering, extraction and disintegration methods are commonly used for sample pretreatment, and visual inspection, spectroscopy and mass spectrometry are used for qualitative/quantitative sample analyses—with field emission Scanning Electron Microscopy (SEM), Confocal Laser Scanning Microscope (CLSM), Raman spectra (Raman), Fourier Transform Infrared Spectrometer (FTIR) and Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS) most commonly used. For complex environmental samples combination methods are often required. Thus this paper summarizes research progress on detection methods for MPs in soils and plants, and discusses the application conditions and advantages and disadvantages of different detection techniques, aiming to provide a scientific reference for future studies, qualitative and quantitative, of MPs in terrestrial ecosystems and MPs transfer and accumulation in plants.

Key words: microplastics, detection methods, soil, plant, emerging pollutants

中图分类号:

刘贺, 宋树贤, 孙梅, 李双双, 于小晶, 戴九兰. 土壤和植物中微塑料研究现状分析及检测方法研究进展[J]. 地学前缘, 2024, 31(2): 183-195.

LIU He, SONG Shuxian, SUN Mei, LI Shuangshuang, YU Xiaojing, DAI Jiulan. Microplastics in soils and plants: Current research status and progress on detection methods[J]. Earth Science Frontiers, 2024, 31(2): 183-195.

图/表 6

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MPs类型	浮选液	分离效果	参考文献
PP,0.89~0.93 g/cm³ PE,0.91~0.94 g/cm³ PS,1.01~1.06 g/cm³ ABS,1.04~1.08 g/cm³ PC,1.18~1.22 g/cm³ PVC,1.16~1.35 g/cm³ PET,1.38~1.41 g/cm³	1. H₂O(1.00 g/cm³) 2. NaCl(1.17 g/cm³) 3. NaBr(1.46 g/cm³) 4. ZnCl₂(1.70 g/cm³)	总提取率: H₂O:47.36% NaCl:89.93% NaBr:96.35% ZnCl₂:95.87% 不同浮选液对低密度MPs呈现良好的提取效果,而高密度 MPs需要选择密度更高的浮选液进行提取	[44]
PE	饱和NaCl	经过后续超声处理后, 最终MPs回收率可达92.9%	[45]
PS、PVC、PE和PET	饱和NaCl+饱和NaI 不同比例混合	总提取率: 当两者比例为1∶1时, 提取效果超过90%, 之后略有升高但逐渐趋于稳定	[46]
PE、PP、PS、PET、尼龙6	82% NaI+0.5%聚乙烯吡咯烷酮(PVP)	加入PVP可将不同粒径,特别是小尺寸MPs的提取率从 60%~70%提高到90%以上	[47]
PE、PP、PET等多种混合	CaCl₂(1.5 g/cm³)	提取率达93%~98%	[48]

MPs类型	浮选液	分离效果	参考文献
PP,0.89~0.93 g/cm³ PE,0.91~0.94 g/cm³ PS,1.01~1.06 g/cm³ ABS,1.04~1.08 g/cm³ PC,1.18~1.22 g/cm³ PVC,1.16~1.35 g/cm³ PET,1.38~1.41 g/cm³	1. H₂O(1.00 g/cm³) 2. NaCl(1.17 g/cm³) 3. NaBr(1.46 g/cm³) 4. ZnCl₂(1.70 g/cm³)	总提取率: H₂O:47.36% NaCl:89.93% NaBr:96.35% ZnCl₂:95.87% 不同浮选液对低密度MPs呈现良好的提取效果,而高密度 MPs需要选择密度更高的浮选液进行提取	[44]
PE	饱和NaCl	经过后续超声处理后, 最终MPs回收率可达92.9%	[45]
PS、PVC、PE和PET	饱和NaCl+饱和NaI 不同比例混合	总提取率: 当两者比例为1∶1时, 提取效果超过90%, 之后略有升高但逐渐趋于稳定	[46]
PE、PP、PS、PET、尼龙6	82% NaI+0.5%聚乙烯吡咯烷酮(PVP)	加入PVP可将不同粒径,特别是小尺寸MPs的提取率从 60%~70%提高到90%以上	[47]
PE、PP、PET等多种混合	CaCl₂(1.5 g/cm³)	提取率达93%~98%	[48]

MPs类型	消解液	消解效果	参考文献
PE	1. 30%H₂O₂ 2. 5mol/L NaOH	H₂O₂:圆形MPs表面有较少的土壤颗粒,回收率89.1%; NaOH:表面附着一部分土壤颗粒、有机质等杂质,回收率90.7%	[45]
PVC、PET、PP等	1. 30%H₂O₂ 2. 10%KOH 3. Fenton	30%H₂O₂普适性较大,Fenton适合在低有机质土壤使用,KOH效果一般	[59]
PS、PE、PET等	混合溶液:15 mL HCl+5 mL HNO₃+3 mL HF	可将0.1 g土壤完全消解并有效提取出多种微塑料	[60]
PE、PP、PET等多种混合	HNO₃	MPs回收率为93%~98%	[48]

MPs类型	消解液	消解效果	参考文献
PE	1. 30%H₂O₂ 2. 5mol/L NaOH	H₂O₂:圆形MPs表面有较少的土壤颗粒,回收率89.1%; NaOH:表面附着一部分土壤颗粒、有机质等杂质,回收率90.7%	[45]
PVC、PET、PP等	1. 30%H₂O₂ 2. 10%KOH 3. Fenton	30%H₂O₂普适性较大,Fenton适合在低有机质土壤使用,KOH效果一般	[59]
PS、PE、PET等	混合溶液:15 mL HCl+5 mL HNO₃+3 mL HF	可将0.1 g土壤完全消解并有效提取出多种微塑料	[60]
PE、PP、PET等多种混合	HNO₃	MPs回收率为93%~98%	[48]

检测技术	方法仪器	所得信息	优缺点
目检法	肉眼观察	尺寸、丰度	可识别1~5 mm大型MPs,对于尺寸微小塑料识别精度低
	常规显微镜	尺寸、丰度	可识别尺寸>100 μm的MPs,经济、简单,但精度低,需辅以染色技术
	电子显微镜	尺寸、丰度	可识别尺寸<100 μm的MPs,检测精度更高,但耗时耗力,测样量少
光谱法	Raman	尺寸、丰度、成分	适合识别尺寸>1 μm的MPs,成像快速、简便,分辨率高;不适用于检测含有荧光的样品,受有机质影响较大,需要提前对样品进行消解
	FTIR	尺寸、丰度、成分	适合识别尺寸>20 μm的MPs,分辨率高、扫描快、精确度高;对样品的颜色、尺寸和其中水分的干扰比较敏感,样品需要提前消解
	TOF-SIMS	尺寸、成分、丰度	质谱多组分同时检测、样品前处理简单、抗干扰能力强
	LDIR	尺寸、丰度、成分	适合尺寸>20 μm MPs的检测,准确度高,节省人力物力,有广阔的发展前景;光谱范围窄(975~1 800 cm^-1)
	THz	预测MPs浓度	穿透性高、能量低、极性分子吸收性强、应用范围广;样品需要保持干燥,检测上下限待确定
质谱法	Py-GC/MS	成分、质量	灵敏性高,可定性定量多种聚合物和添加剂;会受到操作温度和进样量的限制,对MPs具有破坏性
	TED-GC/MS	成分、质量	处理时间相对较短,处理样品量相对较大,但容易受到添加剂、有机物等的影响
	TGA-DSC	成分、质量	适合含结晶结构的聚合物(如PS)
	ICP	尺寸、丰度、成分、质量浓度	适合检测尺寸为1~10 μm的MPs,适用于个人护理产品和食品包装材料释放的MPs的筛查