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塑料是从石油或天然气中提取的单体聚合而成的高分子化合物[1-2]. 自1907年第一种现代塑料“酚醛塑料”问世以来,塑料便因轻质、耐用、价廉和耐腐蚀等特性广泛应用于生产生活中[3]. 这些特性恰好是塑料对环境造成严重危害的原因之一,塑料消费需求的增加导致了大量的塑料污染. 2004年,英国学者Thompson首次提出“微塑料”的概念,并发现微塑料在海洋水体沉积环境中十分常见[4],后来的研究人员将微塑料定义为粒径小于5 mm的塑料碎片. 根据不同来源微塑料可分为初生微塑料和次生微塑料. 初生微塑料是指工业生产过程中直接排放的微观尺寸的塑料颗粒;次生微塑料是指较大的塑料进入环境中经过分解、破裂形成微型的塑料碎片[5-6]. 微塑料体积小,化学性质稳定,可存在数百上千年,且易吸附多种微生物和化学污染物,被海洋动物摄食后进入食物链,进而影响人体的消化功能[7-9].
近年来微塑料污染受到人们的研究和关注,已有的研究表明在海洋、湖泊、土壤、大气和生物体中均存在微塑料[9-12]. 其中对海洋、湖泊、土壤的研究总结较为深入,检测技术也比较成熟,对大气环境的研究较少. 本文对不同研究中大气环境微塑料的来源、分类、提取方法、检测技术、已有的研究进展进行综述,以期为未来的微塑料研究提供参考.
大气环境中微塑料污染及其分析技术的研究进展
Progress on microplastics pollution and its analysis methods in the atmosphere
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摘要: 微塑料污染物(直径小于5 mm的塑料碎片)对生态环境的潜在影响已成为人们关注的热点问题之一. 现有的研究微塑料的文献大多集中在水生环境,尤以海洋环境中的微塑料研究居多. 有关大气环境系统中微塑料污染近几年才受到关注. 本文综述了近年来有关大气微塑料研究的最新进展,概括了大气微塑料的来源及分类. 此外,归纳了目前常用于大气环境中微塑料的采集方法,并进一步列举了不同采集方法可适用的提取、分析方法,指出不同方法的优缺点. 最后,在总结国内外研究进展的基础上,对我国大气环境微塑料研究提出建议:①为使研究结果具有可对比性,大气环境微塑料的丰度单位需统一;②大气微塑料远距离传输的转化和降解过程需要进一步的研究;③微塑料在正常环境下的暴露对人体的危害需要更深入的了解.Abstract: Microplastics (plastic debris with diameter less than 5 mm) have become a hot topic due to their ubiquity in our living environment and potential impact on the ecological environment. Previous literature mainly focused on microplastics in the aquatic environment, especially in the marine environment, only a limited number of papers studied microplastics in the atmosphere. Here, we review the latest research progresses, the source, and the classification of atmospheric microplastics. Moreover, we compare the extraction procedures of different collection methods, summarize the commonly used methods for the analysis of atmospheric microplastics, and evaluate their advantages and disadvantages. Finally, further suggestions are on future microplastic research are proposed: ①The unit of microplastics in the atmosphere should be unified, in order to ensure the comparability of future studies. ②Further studies are required on the transformation and degradation processes of atmospheric microplastics during long-range transport. ③It is necessary to evaluate the potential health threat of microplastic exposure in our living environments.
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Key words:
- atmospheric environment /
- microplastic /
- extraction methods /
- analysis methods
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表 1 不同采样方法
Table 1. Different methods for collection of microplastics
采样方法
Collection methods适用丰度单位
Suitable unit适用条件
Suitable conditions优点
Advantage缺点
Disadvantage干湿沉降 个·m-2·d-1 被动采样,无需供电,适用于各类环境 自然沉降更客观的反映微塑料丰度 需要较长时间的观测,时间分辨率低 大气采样 个·m-3 主动采样,适用于供电方便地区,偏远无供电地区不适用 可以主动采集悬浮在空中的微塑料 收集到的样品杂质较多,雨天不易收集 粉尘收集 个·m-2,mg·g-1,个·kg-1 室内外各类灰尘聚集区域 可以观测已沉降的微塑料,采样简便 无法对悬浮在大气中的微塑料进行估计,样品杂质也较多 表 2 不同提取方法
Table 2. Different methods for extraction of microplastics
提取方法
Extraction methods适用采集方法
Applicable methods存在问题
Disadvantage目检法 三种方法均可 误判、漏数等原因使准确性受影响 密度分离法 干湿沉降、粉尘收集法 不足以去除全部有机质 消解法 三种方法均可 部分酸性溶液会消解部分类型微塑料 过滤干燥 干湿沉降 过滤及转移过程中会存在部分样品损耗 表 3 不同分析技术汇总
Table 3. Summary of different methods for analysis of microplastics
检测技术
Analysis methods介绍
Introduction优点
Advantage缺点
DisadvantageStereomicroscope[5] 通过形貌观察对样品进行分析 操作简便,检测过程快 对尺寸小于1 mm的微塑料易造成误判 micro-FT-IR[51,53] 通过检测化学键、官能团的振动吸收,
分析样品类型。操作简便,样品无需特殊处理,与Raman技术互补 易受环境影响,检测过程耗时耗力 micro-Raman[51,53] 通过激光激活分子振动,测量分子结构 操作简便,样品无需特殊处理,与FT-IR技术互补 结果受激发光波段选择影响,检测过程耗时耗力 SEM-EDS[29] 通过电子束与样品的相互作用,测量样品表面形态与元素 可精确检测样品表面形貌和成分 前处理过程易损毁样品,时间和人工成本较高 Fluorescence microscope[37,48] 通过染色剂将样品染色以观察,增强识别样品的客观性 与目检法互补,挑拣微塑料样品成功率高 无法对微塑料的种类进行具体分析 Pyr-GC-MS[38,55] 通过高温加热使样品热裂解,经气相色谱分离后,由质谱进行分析鉴定 样品用量小,不需要预处理,可同时鉴定聚合物和塑料表面添加剂 无法分析微塑料的大小、形状和数量,实验条件要求高,对样品的破坏性强 表 4 不同地区的研究情况
Table 4. Studies on microplastics in different areas
采集地点
Site采集年份
Year采集方法
Collection methods提取方法
Extraction methods检测技术
Analysis methods种类
Types丰度范围
Concentration range烟台[25] 2014 干湿沉降 目检、消解 micro-FT-IR 纤维、碎片、薄膜和发泡 1.30×102—6.24×102 个·m−2·d−1 巴黎[18] 2014 干湿沉降 过滤干燥 SEM-EDS 纤维、碎片 2.90×10—2.80×102 个·m-2·d−1 巴黎[14] 2014-2015 干湿沉降 过滤干燥 micro-FT-IR 纤维 2.00—3.55×102 个·m−2·d−1 东莞[24] 2016 干湿沉降 过滤干燥 micro-FT-IR 纤维、碎片、薄膜和发泡 1.75×102—3.13×102 个·m−2·d−1 巴黎[17] 2016 大气采样 目检 micro-FT-IR 纤维 0.3—5.94×10 个·m−3 日本[40] 2017 粉尘收集 密度分离、过滤干燥 micro-FT-IR 纤维、碎片、薄膜 (2.0±1.6)个·m−2 中国39个城市[59] 2017-2018 粉尘收集 目检、密度分离、过滤干燥 micro-FT-IR 纤维 4.6×10-3—2.7×10 mg·g−1 北京[46] 2018 大气采样、干沉降 目检 SEM-EDS 纤维 5.7×103 个·m−3 伦敦[36] 2018 干湿沉降 过滤干燥 micro-FT-IR、Fluorescence microscope 纤维、薄膜 5.10×102—9.25×102 个·m−2·d−1 上海[26] 2018 大气采样 目检 micro-FT-IR 纤维、碎片、薄膜 0—4.18 个·m−3 维多利亚[31] 2018 粉尘收集 目检、消解、过滤干燥 Stereomicroscope、 micro-FT-IR 纤维、碎片 20.6—529.3 个·kg−1 美国11个自然保护区和偏远地区[60] 2017—2019 干沉降和湿沉降 过滤干燥 micro-FT-IR 纤维 132 个·m−2·d−1 阿威罗[43] 2019 大气采样 目检、密度分离、过滤干燥 Stereomicroscope 纤维、碎片 5—6 个·m−3 表 5 近几年微塑料对人体危害的研究
Table 5. Recent studies on the health effects of microplastics on human
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