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塑料,因其轻质、耐用、高强度的性能和低廉的成本广泛应用于工农业生产和日常生活中[1] . 据统计,塑料垃圾仅有约 9% 的塑料得以回收,79%的塑料被填埋或者遗弃在自然界中[2-3]. 由于人类对塑料垃圾的不当处理,导致塑料以颗粒或碎片形态在海洋、淡水和陆地环境中不断积累[4-5]. 残留在环境中的塑料碎片经紫外照射、化学分解和微生物降解等一系列过程后,形成尺寸较小的塑料碎片,其中粒径小于5 mm的塑料碎片一般被称为微塑料[6-8].
由于微塑料具有稳定性高、粒径小及迁移性强等特性,能长期存在于环境中,可通过动物摄食、植物富集等方式经食物链逐级传递[9-10];此外还可向环 境中释放增塑剂等助剂[11-12];由于体积小,比表面积大,微塑料对污染物吸附能力很强,产生复合污染效应,对环境和人体健康造成严重危害[13-14] ,进而可引发严重的环境和健康问题. 目前已有研究在人类粪便[15]、血液[16]和肺部[17]发现微塑料. 近年来,塑料和微塑料环境污染问题已经得到国际社会的重视. 在2019年《控制危险废物越境转移及其处置巴塞尔公约》(简称“巴塞尔公约”)第十四次缔约方大会上通过了关于废塑料的修正案,为相关各国的禁塑令提供了充分支撑,并扩大了公约管控的塑料废物的范围. 在第一届和第二届联合国环境大会上,海洋塑料垃圾污染和微塑料污染被接连列入重大全球环境问题. 2022年召开的第五届联合国环境大会,标志性地通过了《终止塑料污染治理全球协议》,治理环境微塑料污染迫在眉睫.
我国是全球塑料生产和消费的第一大国[18],统计结果显示, 1950—2015年间我国塑料产量约占全球总产量的30%[2],我国每年塑料垃圾排放量居全球首位[19]. 当前我国政府十分重视微塑料的污染问题,2022年国务院印发的《新污染物治理行动方案》中,将微塑料明确列为重点新污染物之一. 研究表明陆地中存在的微塑料丰度可能是海洋的4—23倍[20]. 然而,作为环境中微塑料的最大储库,土壤中微塑料的研究尚处于起步阶段,对微塑料的来源、环境归趋、污染状况和生态风险知之甚少,我国土壤中微塑料治理面临污染状况不明、风险不清的现实问题.
本文梳理了国内外土壤环境中微塑料相关研究成果,系统介绍国内外土壤中微塑料赋存水平和污染特征,着重阐述国内外土壤中微塑料主要的检测技术研究现状和最新进展,分析土壤中微塑料的分离、杂质去除和定性定量分析主流方法的优缺点和适用范围,提出土壤中微塑料污染调查和检测技术研究方向,以期为土壤中微塑料风险管控提供技术支撑和科学依据.
土壤中微塑料污染现状与检测技术研究进展
Research progress on pollution status and analysis method for microplastics in soil
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摘要: 微塑料一般是指粒径小于5 mm的塑料碎片,作为一种新污染物已经成为全球环境领域的研究热点. 土壤作为环境中微塑料的最大储库,土壤中微塑料的污染逐渐引起重视并取得了一定的研究进展. 本文系统了梳理了国内外土壤中微塑料的污染现状和污染特征,介绍了土壤中微塑料检测技术研究进展,重点探讨各类样品采集、前处理和和定性定量方法的优缺点以及对土壤中微塑料检测的适用性,分析了土壤中微塑料检测技术研究面临的主要挑战,提出未来土壤中微塑料污染调查与检测技术的研究方向,以期为科学开展土壤中微塑料污染风险治理与管控提供技术支撑.Abstract: Microplastics are plastic particles with size less than 5 mm. As an emerging pollutant, microplastics become the research focus globally. Soil has been regarded as the largest reservoir of plastics and microplastics pollution in soil has arouse global concern and has achieved progress recently. In this study, research progress of pollution extent and pollution characteristics for microplastics in soil both at home and abroad had been systematically investigated. Current situation on analysis techniques of microplastics in soil were reviewed. Advantages, disadvantages as well as the applicability of separation, purification, identification and quantification methods of soil microplastics were discussed. Challenges in the analysis of microplastics in soil and suggestions on the research directions on soil microplastics were proposed, which could provide technical support for the risk management and control of soil microplastic pollution.
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Key words:
- microplastics /
- soil /
- pollution characteristics /
- analysis techniques /
- method standard /
- technical specification.
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表 1 国外土壤中微塑料污染状况汇总
Table 1. Microplastics in soil of foreign countries
国家
Country研究区域
Region土地利用类型
Land use type形态
Shape聚合物类型
Polymer composition尺寸/mm
Size丰度/(个·kg−1)
Abundance点位个数与布点方法
Number of sites and method样品采集方法
Sampling method样品保存条件
Storage condition采样深度/ cm
Sampling depth参考文献
Reference西班牙 巴伦西亚 污泥施用农田普通农田 碎片>纤维>薄膜 930 ± 740a,1100 ± 570b,2130 ± 950c,3060 ± 1680d 16个 单独样 PP密封袋 0—1010—30 [25] 智利 梅丽皮亚县 污泥施用农田 纤维 <2 1.1—3.5e 简单随机 单独样 PP密封袋 25 [36] 西班牙 穆尔西亚 覆膜菜地 2116± 1024 单独样 10 [31] 韩国 京畿道 水稻田 碎片>薄片>纤维 PE > PP 0.2—0.3 160 ± 93 混合样 不锈钢盒 5 [30] 覆膜农田 纤维 >碎片>薄片 PP > PE >PS > PET 1.0—2.0 81 ± 77 温室内 碎片 >纤维>薄片 PE > PET> PP 0.1—0.2 1880 ± 1563 温室外 纤维 >薄片>碎片 PP > PE >PET 0.2—0.3 1302 ± 2389 瑞士 洪泛平原 湿地土壤 PE>PS>PP 0—5 0—593 29个 混合样 铝盒 5 [29] 印度 尼特雷迪河 河滨土壤 纤维>薄膜>碎片 PE>PET>PP 0.3—5 84.45 单独样 5 [28] 西班牙 地中海 海草土壤 68—8832 [27] 澳大利亚 悉尼 工业用地 PVC>PE>PS 0—1 300—67500 17个 [32] 伊朗 阿瓦士市 城市土壤工业土壤 纤维 PET>尼龙 100—3135,80—122 21个 混合样 密封玻璃罐 [33] 韩国 京畿道骊州市 林地城市用地农用地 碎片>薄膜>纤维 PE>PP 0—5 700 100个网格布点 不锈钢盒 0—5 [34] 智利 中央山谷 粮食产地草场牧场天然草地 纤维>薄膜>碎片 丙烯酸树脂(ACR)>聚醚砜树脂(PES)>尼龙>PVC — 306 ± 360,184 ± 266
—
—240个 [11] 德国 北部 农田 薄膜>碎片>薄片 PE>PP>尼龙>PA 1—5 0—217.8 15个 玻璃瓶 0—10
10—20
20—30[35] 注:a,未施用污泥农田中轻质微塑料(ρ<1.0 g·cm−3)丰度;b,未施用污泥农田中重质微塑料丰度(ρ>1.0 g·cm−3);c,施用污泥农田中轻质(ρ<1.0 g·cm−3)微塑料;d,施用污泥农田中重质微塑料丰度(ρ>1.0 g·cm−3);e,单位是mg·kg−1. Note: a, load of light density(ρ<1.0 g·cm−3) microplastics in soils without addition of sewage sludge; b, load of heavy density(ρ>1.0 g·cm−3) microplastics in soils without addition of sewage sludge. c, load of light density(ρ<1.0 g·cm−3) microplastics in soils with addition of sewage sludge; d, load of heavy density(ρ>1.0 g·cm−3) microplastics in soils witht addition of sewage sludge. e, unit was mg·kg−1. 表 2 我国土壤中微塑料污染状况汇总
Table 2. Microplastics in soil of China
研究区域
Region土地利用类型
Land use type形态
Shape聚合物类型
Polymer composition尺寸/mm
Size丰度/(个·kg−1)
Abundance点位个数
与布点方法
Number of sites
and method样品采集方法Sampling method 样品保存条件
Storage condition采样深度/cm
Sampling depth参考文献
Reference新疆石河子 覆膜农田 薄膜 PE 0.007—5 mm 80.3 ± 49.3a
308 ± 138.1b
1075.6 ± 346.8c15个
简单随机混合样 铝箔袋 0—3
3—6[40] 山东寿光 设施农业土壤
露天农业土壤碎片>薄膜>纤维
>小球>泡沫PP>乙烯丙烯酸共聚物(EAA)>PE>PS>PET 0—5 310—5698 45个 混合样 0—5
5—10
10—25[53] 西藏、云南、
四川、青海温室农田
覆膜农田
耕地草地薄膜>碎片>纤维 PE>PA>PS>PP 0—2 53.2 ± 29.7
43.9 ± 22.3混合样 铝箔袋 0—3
3—6[41] 陕西 农田 纤维 PS>PE>PP>高密度聚乙烯(HDPE)>PVC>PET 0—5 1430—3410 9个分块随机 混合样 不锈钢瓶、冰箱冷藏 [54] 新疆阿拉尔市 覆膜棉花田 碎片>纤维>颗粒 0—5 161.50±5.2d 11.20±1.10d 100个 混合样 布袋 0—30(每层5 cm,共6层) [38] 湖北武汉 菜地 纤维>微珠 PA>PP 0—5 320—12560 20个 混合样 铝盒,冷藏(<4℃) 0—5 [45] 云南滇池流域 菜地 纤维碎片薄膜 0.05—10 mm 7100—42960 25个 混合样 0—5
5—10[55] 内蒙古河套地区 灌区农田 纤维>碎片>薄膜>颗粒 0—5 678.00—2133.50 6个分块随机 单独样 采样袋 0—10
10—20
20—30[39] 沈阳周边 农田 薄膜>碎片>纤维>颗粒 PE>PP>PS 0—5 217.30—2512.18e 84个 混合样 自封袋 0—5
5—10
10—20
20—30[43] 大辽河流域 居民区、农田 薄膜>碎片>泡沫 PE>PP>PS>PA 0—5 273.33±327.65 铝箔、PE自封袋,冷藏(<4 ℃) [44] 上海郊区 菜地 纤维>碎片>薄膜 PP>PE 0.02—5 78.00 ± 12.91
62.50 ± 12.9720个 铝盒 0—3
3—6[46] 广东贵屿 电子垃圾拆解区 颗粒>碎片>薄膜>
纤维>圆球>圆柱PS>PP>聚乙烯醇(PVAL) 0—5 9450±9520 11个简单随机 单独样 铝箔袋 20 [42] 北京市区 塑料防尘网覆盖区 纤维>颗粒>碎片>薄膜 PE 0—2 272—13752 5个简单随机 混合样 铝盒,冷藏(<4 ℃) 2 [48] 北京郊区 遗弃温室
常规温室
简易温室碎片 PP>PE 0—5 2215.56 ±1549.86
891.11 ± 316.71 632.50 ± 566.9314个 混合样 铝箔
冷藏 (<4 ℃)0—10
10—20[58] 青藏高原 温室 纤维>碎片>薄膜 PC>PE>PP>PS 5—340 85个带状抽样 铝盒(<4 ℃) 0—5 [59] 注:a,覆膜时间5年;b,覆膜时间10年;c,覆膜时间24年;d,单位为个·100g−1;e,单位为µg·g−1.
Note: a, mulchin time was 5 a; b, mulching time was 10 a; c, mulching time was 24 a; d, unit was ind·100g−1; e, unit was µg·g−1.表 3 微塑料主要分析技术
Table 3. Analysis methods of microplastics
分析技术
Analytical technique检测原理
Test principle适用范围
Scope of application获取信息
Information obtained存在问题
Disadvantages显微镜观察法 光学放大,人工挑拣 可用于100 μm以上微塑料检测 形态信息、丰度 简单方便,但耗人力,且在微塑料材质鉴别上准确度较低 傅里叶红外光谱法(FTIR) 利用不同塑料材质的特征红外
干涉光谱进行样品识别.
光谱范围400—4000 cm−1可用于20 μm以上的微塑料检测. 傅里叶红外光谱仪是市场占比最多的设备 形态信息、化学成分、丰度 需要用显微镜人工挑选,再红外光谱逐一定性,检测周期长 拉曼光谱法(Raman) 利用不同塑料材质的特征拉曼
散射光谱进行样品识别. 光谱
范围50—3000 cm−12 μm以上的微塑料. 不受测量颗粒形状、大小或厚度等干扰 形态信息、化学成分、丰度 会受到具有荧光效应的有机物干扰. 运行时间较长,不适用于批量检测 激光红外光谱法(LDIR) 利用不同塑料材质的特征红外
激光光谱进行样品识别. 光谱
范围900—1800 cm−120—500 μm的微塑料检测,可以连续扫描. 检测效率非常高,适用于批量样品测试 形态信息、化学成分、丰度 光谱范围相对较窄,仪器价格相对较高 热分析法 利用热裂解技术等使微塑料
分解,然后利用质谱检测适合单一组分的塑料检测,前处理简单,灵敏度高 质量含量、化学成分 难以分辨质量和降解温度数据相似的复合物,尤其是成分复杂、纯度不高的回收塑料 液相色谱(串联三重四级质谱)法(HPLC/LC- MS/MS) 选择性解聚或制备样品以供
分离和定量适合单一组分的微塑料解聚物的检测,前处理简单,灵敏度高 质量含量、化学成分 仅限于特定的聚合物,对土壤实际样品的适用性尚需验证. 表 4 我国环境介质中微塑料监测标准
Table 4. Method standards of China for microplastics in environmental matrix
环境介质
Environment matrix标准类型
Standard category监测标准
Method standard海 洋 生态环境行业标准 《海洋微塑料监测技术规程(试行)》(制定中) 地方标准 《海水中微塑料的测定 傅里叶变换显微红外光谱法》(DB21/T 2751—2017) 地方标准 《海水增养殖区环境微塑料监测技术规范》
(DB37/T 4323—2021)地表水 团体标准 《地表水中微塑料的测定》(制定中) 景观水 团体标准 《景观水中微塑料的测定 傅里叶变换显微红外光谱法》(T/CSTM00563—2022) -
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