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作者简介:

孙飞虎(1998-),在读硕士研究生,主要从事土壤微塑料及资源利用与植物保护研究。E-mail:704217508@qq.com。

通讯作者:

王鑫鑫,E-mail:sywxx@hebau.edu.cn。

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目录contents

    摘要

    塑料在全球范围内大量使用,产生的微塑料对环境系统构成了潜在的威胁和不可预测的风险。土壤中微塑料的研究由于受到土壤基质复杂和微塑料来源多样的制约,面临很多困难。通过回顾有关微塑料污染及其对土壤生态系统的影响,解析了现在所面临的土壤微塑料污染问题,并针对土壤中微塑料的来源、分析检测方法,以及微塑料对土壤生态系统的影响进行了总结汇总。在此基础上对土壤微塑料污染研究进行了展望,并探讨分析了未来该领域的主要研究方向和防控措施。

    Abstract

    Plastic is widely used in the world,and the microplastics generated pose a potential threat and unpredictable risk to the environmental system. The research of microplastics in soil is faced with many difficulties due to the complex soil matrix and the diverse sources of microplastics. Based on reviewing the microplastic pollution and its effects on soil ecosystem,we analyzed the problems of soil microplastic pollution that China is facing now. The sources,analysis and detection methods of microplastics in soil,and the impact of microplastics on soil ecosystem were summarized. On this basis,the prospect of soil microplastic pollution research was made,and the main research direction and prevention and control measures in this field were discussed.

  • 塑料是单体通过加聚或缩聚反应聚合而成并通过加入某种化学物质改变其性能的高分子聚合物。由于其价格低、耐久性好、质量轻、延展性好,被广泛应用于日常生活的各个方面[1]。塑料在长期的物理、化学、生物作用下逐渐分解成无数个小的塑料颗粒、纤维、碎片等,其中直径小于5mm的归为微塑料[2]。根据其来源不同,微塑料又可被细分为初级微塑料和次级微塑料。初级微塑料是指在塑料生产过程中产生的塑料颗粒、塑料纤维等,次级微塑料是指塑料制品或塑料垃圾进入自然环境后分化形成的微小塑料碎片[3]。目前环境中微塑料的形貌类型主要有薄膜、碎片、纤维、颗粒和发泡等[4]。常见的微塑料聚合物类型有聚丙烯(PP)、聚乙烯(PE)、聚对苯二甲酸乙二醇酯 (PET)、聚氯乙烯(PVC)、聚苯乙烯(PS)、聚酰胺(PA)、聚乳酸(PLA)等[5-6]。由于塑料使用量压倒性的增加,污染问题加重,微塑料污染问题正在引起全球的重视。

  • 调查显示,1950至2015年间,全球的塑料废弃物估计有63亿t[7]。2019年,全球塑料制造总量约为3.6×108 t [8]。如果塑料消费和全球生产持续增加,微塑料污染造成的环境破坏将会更加严重[9]。我国土壤微塑料污染的来源有农业地膜的使用、污泥和有机肥的施用、地表水灌溉和大气沉降等方式[4]。 Qi等[10]预测,到2025年,中国的塑料产量将达到2.28×106 t。大块塑料经紫外线照射、碰撞磨损等方式破碎形成粒径小于5mm的固体颗粒或纤维[11]。在复杂的非均质土壤系统中,微塑料来源于多种复杂的生态途径和环境循环,可能产生各种生态压力[12]。其在土壤中的丰富性、持久性和无处不在,象征了一种严重的环境风险[13]。土壤提供了生命所必需的广泛生态系统服务,同时也是微塑料的重要储存库[14-15],因此微塑料的分解方法及对土壤影响的作用机制成为我国目前亟待解决的问题。而现今关于土壤微塑料的研究还处于起步阶段,因此研究土壤中的微塑料具有重要意义。

  • 1 我国微塑料污染现状

  • 我国是全球塑料使用量最高的国家,由于对塑料回收利用的政策还不完善,大量塑料废弃物进入环境中。水体是微塑料汇聚迁移的地点,我国辽河流域土壤中微(中)塑料的丰度范围在 (13.33±11.55)~(886.67±133.17)个/kg之间[16]。汾河上、中游沿岸农田土壤中微塑料丰度均值为213.8个/kg[17],天津近海岸海水样品微塑料丰度在210~1170个/m3 之间[18]

  • 全国范围内不同地区不同利用类型土壤都具有不同程度的微塑料污染。我国武汉地区土壤微塑料丰度为2.2×104~6.9×105 个/kg[19]。Liu等[20] 在上海郊区的20块菜地农田土壤中发现浅层土壤和深层土壤微塑料丰度分别为(78.00±12.91)和 (62.50±12.97)个/kg,其中<1mm的微塑料分别占其组分的48.79%和59.81%。Zhou等[21] 调查了我国渤海和黄海沿岸土壤中微塑料的分布,发现土壤微塑料的浓度为1.3~14712.5个/kg。Ding等[22]在我国西北地区毛乌素沙地土壤中观察到薄膜、颗粒、碎片和纤维4种类型微塑料,平均含量为2697个/kg。高污染地区通常有典型的污染源或长期使用塑料薄膜覆盖,如我国云南滇池一个农田区域的微塑料浓度较高,平均为18760个/kg[23]。Yu等[24]在我国北方最大的温室蔬菜生产基地山东省寿光市采集设施农业土壤、露地农业土壤和农用塑料地膜样品测得所有采样点3个土壤层的微塑料丰度范围为310~5698个/kg,平均值为(1444±986)个/kg,主要形状是碎片和薄膜。Han等[25]在天津(我国北方)校园草坪土壤中检测出PP微塑料75个/kg。

  • 废弃物处理区由于塑料富集导致土壤微塑料污染尤为严重,Chai等[26]在我国贵屿镇一个电子垃圾分解区观察到,不同土地利用方式下的土壤中微塑料的丰度差异很大,范围在0~34100个/kg之间。潘琪等[27]研究在莱州市沙河镇废旧塑料再生基地内部及周边区域采集土壤样品,检测得出废弃塑料再生地农田土壤中6种邻苯二甲酸酯(PAEs) 总量介于4.63~15.59mg/kg之间,参考美国土壤PAEs控制标准,其中的邻苯二甲酸二甲酯、邻苯二甲酸二乙酯和邻苯二甲酸二丁酯超标严重。

  • 由上可知,微塑料已经遍布我国各地区,涉及各种利用类型土壤,土壤微塑料污染问题亟待解决。但目前还仍未建立统一的土壤中微塑料污染检测指标和有效的污染治理技术,这是未来必须要面临解决的问题。

  • 2 土壤中微塑料的来源

  • 土壤中的微塑料是人为生产的塑料制品以不同的携带方式直接或破碎后进入土壤环境。其来源主要有:

  • (1)农业地膜覆盖残留的微塑料。农用塑料覆膜其主要材料是PE,PE膜在自然条件下不易降解[28-29],这些被包裹在土壤中的塑料薄膜在耕作、紫外线辐射和微生物降解的帮助下,慢慢分解成微塑料[26]

  • (2)有机肥中携带的微塑料。Bläsing等[30]在德国波恩某堆肥厂中的3个有机肥样品中,目检发现塑料碎片,其含量为2.38~180个/kg。Yang等[31]研究发现施用猪粪后的土壤与未经改良的土壤相比,土壤中微塑料的含量显著增加,长期施用猪粪的农业土壤中,塑料微粒的平均累积速率为 (3.5±1.7)×106 个/(hm2 ·年)。

  • (3)污水污泥中的微塑料。污水污泥是农业系统中微塑料的重要来源[32]。Li等[33]通过对我国11个省市28家污水处理厂79份污泥样品进行分析,研究污泥中微塑料的存在情况。结果得出干污泥样品中的微塑料浓度为1.60×103~56.4×103 个/kg,平均为(22.7±12.1)×103 个/kg。

  • (4)地表径流和农田灌溉引进土壤中的微塑料。地表径流和农田灌溉会将大量微塑料带入土壤中[34]。耿世雄[35] 研究得出长江中下游18个湖泊表层水中微塑料的含量范围为240~1800个/m3,平均丰度为(780±429)个/m3。徐沛[36]在长江口和东海区域共检测出3225块微塑料(60~5000 μm),浓度分别为(157.2±75.8) 和(112.8±51.1)个/m3

  • (5)垃圾填埋进入土壤的微塑料。生活垃圾、城市垃圾等填埋场是微塑料的潜在产生源[37],如纺织品外套、人造毛皮含有微纤维[38],个人护理产品,如洗面奶和牙膏,含有大量的初级微塑料[39],烟熏过滤器和未吸剩余烟草含有微纤维[40]

  • (6)大气沉降的微塑料。Dris等[41]研究结果显示,大气沉降物中含有大量纤维,表明大气沉降是微塑料的一个不可忽视的潜在来源。

  • (7)其他来源的微塑料。道路和轮胎碎片,也是土壤微塑料的来源之一[42]。鸟类等迁徙类动物也可以作为微塑料长距离运输的载体,对微塑料的迁移及扩散起到一定作用[34]

  • 3 微塑料对土壤生态系统的影响

  • 目前,全球范围内对塑料的需求量大,由于回收利用措施不完善,大量塑料经填埋处理,产生大量性质稳定、难降解、易挥发的塑料垃圾衍生物微塑料,广泛富集于土壤中,与土壤有机质发生相互作用,被土壤中微生物吸收,并且还会与土壤中的物质发生吸附作用,进而改变土壤的物理化学性质,影响土壤中的养分循环。

  • 3.1 微塑料对土壤理化性质的影响

  • 由于微塑料表面的特殊性质,其会与环境中一系列不同疏水性的有机化学物结合,例如多环芳烃、多氯联苯、多溴二苯醚、二恶英和金属[43],形成复合污染物。Yu等[44]研究结果显示,土壤中粒径为100 μm的PE存在促进重金属(Zn、Cu、 Ni、Cd、Cr、As、Pb)从生物有效态向稳定有机结合态的转化,降低了其生物可利用性。微塑料影响土壤团聚体的形成、稳定和分解过程[45]。刘亚菲[46]研究得出土壤水稳性微团聚体中微塑料含量显著高于大团聚体,微塑料含量高的微团聚体难以被团聚成大团聚体,因此微塑料的存在会破坏土壤结构,造成土壤表面干燥开裂。Machado等[47]研究发现,不同类型的微塑料对土壤产生的影响不同,如聚酯可降低土壤水稳性团聚体的量,而PE则显著提高了土壤水稳性团聚体的量。

  • 微塑料进入土壤会导致土壤养分、水分水平发生变化。微塑料薄膜可以形成水通道,使水迅速渗透到深层土壤中,并且这些薄膜还会导致表层土壤出现干燥裂缝,也可以通过创造水运动通道来加速土壤水分蒸发[48]。Seeley等[49]通过对比添加聚氨酯和PLA的沉积物与没有微塑料的对照沉积物发现,添加聚氨酯和PLA的沉积物促进硝化和反硝化,而添加PVC抑制这2个过程。Dong等[50] 通过研究微塑料(PS和聚四氟乙烯)和As对水稻根际土壤的影响发现,As、PS和聚四氟乙烯会与酶结构中的氨基酸残基相互作用,土壤脲酶、酸性磷酸酶、蛋白酶、脱氢酶和过氧化物酶的活性受到抑制,从而降低土壤有效N和P的含量。Yu等[51]通过长期培养试验发现,PE微塑料污染下土壤中N、P、K、可溶性有机C、Olsen-P和可溶性有机N含量下降,导致土壤养分水平下降。Hou等[52] 研究发现,PE微塑料的存在显著改变了土壤阳离子交换量、全N含量、溶解有机C和Olsen-P含量,改变了不同土壤团聚体组分的物理化学性质,且显著性随着土壤团聚体尺寸的变化而变化。Li等[53]采用逐级化学提取和生物学方法研究了土壤重金属的生物有效性。结果表明,PE微塑料降低了土壤对金属(Cu2+ 和Ni2+)的吸附能力,提高了土壤中金属(Cu2+ 和Ni2+)的可交换性和生物有效性。

  • 3.2 微塑料对土壤微生物的影响

  • 微塑料对土壤微生物的影响与其粒径、类型和浓度有关。Fei等[54]研究发现添加低浓度(1%w/w)、高浓度(5%w/w)PE和高浓度(5%w/w) PVC能显著提高变形杆菌目(Betaproteobacteriales) 和假单胞菌目(Pseudomonadales) 的相对丰度,而添加低浓度(1%w/w)PVC则轻微降低这2个菌群相对丰度。添加PVC后弗兰克氏菌目 (Frankiales)和丙酸杆菌目(Propionibacteriales)丰度升高,而添加PE后丰度降低。Feng等[55]通过研究0.2%和2%(W/W)浓度下不同类型MPs对微生物的影响发现,浓度为2%时,会明显降低细菌群落的丰度和多样性,并改变微生物群落组成。丛枝菌根真菌是近年来的一个研究热点,微塑料对丛枝菌根真菌的影响与其类型、浓度、粒径有关。Wang等[56]通过试验发现,PE对丛枝菌根真菌的多样性没有影响,但是大大改变了它们的群落结构,而PLA对丛枝菌根真菌多样性和群落组成均有显著影响。张晓晴[57]研究得出,微塑料粒径和浓度显著影响了丛枝菌根真菌的物种组成。Lehmann等[58]观察到聚酯微塑料能够促进丛枝菌根真菌和菌丝圈的定殖。微塑料被证实可以改变土壤微生物群落组成。Cheng等[59]研究发现PP微塑料对土壤细菌多样性和细菌群落结构有明显的影响,其中,气单胞菌科(Aeromonadaceae)和假单胞菌科(Pseudomonadaceae)的相对丰度显著增加,而亚硝基球菌科(Nitrososphaeraceae)和变形杆菌门(Proteobacteria)的2个未知科的相对丰度显著减少。Yan等[60]研究发现,PVC微塑料虽然对整个细菌群落无显著影响,但对某些细菌类群的丰度有显著影响。Wang等[61]利用线性判别分析的方法来确定对照组和微塑料暴露组之间丰度的显著差异,结果显示微塑料选择性地富集了土壤样品中的特定细菌成员。Ng等[62]的研究显示,在添加PET(施用量分别为0.2%和0.4%)和低密度PE(施用量较高时为3%)42d后,土壤细菌群落的均匀度和丰富度降低。Seeley等[49]研究发现,微塑料的存在可以改变沉积物微生物群落组成,对照组中染色菌科(Chromatiaceae)、外硫红螺旋菌科(Ectothiorhodospiraceae)、慢微生物科 (Lentimicrobiaceae)、磁球菌科(Magnetococcaceae)、小梨形菌科(Pirellulaceae)、Sedimenticolaceae(暂译为沉香科)、嗜热厌氧菌科(Thermoanaerobaculaceae) 和沃斯菌科(Woeseiaceae)[63]的相对丰度明显高于PVC处理。Guo等[64]研究发现,土壤中加入聚酯超细纤维对土壤微生物群落的多样性和组成影响不大,而附着在聚酯超细纤维上的细菌群落比附着在周围土壤上的细菌群落更为多样。Lozano等[5]研究发现,土壤中添加浓度较高的微塑料纤维导致微生物活性降低,如0.3%(w/w)的PA和聚酯、0.4%(w/w)的PP,而土壤中添加低浓度的0.1%(w/w) PA纤维,与对照相比增加了微生物的活性。Gao等[65]通过试验发现,微塑料添加处理与对照处理相比,土壤微生物生物量、微生物群落活性和土壤CO2排放量增加,并指出微塑料引起的土壤呼吸增加可能是由于生物量和微生物活性的增加以及微生物对微塑料添加压力的反应。在这些研究中,聚合物的形状、类型、浓度和大小等参数都是不同的,因此不能根据单个变量来归纳出微塑料对微生物活性的毒性效应,更重要的是人工干预状态下微塑料的浓度可能不能代表与实地相关的条件[66]

  • 3.3 微塑料对土壤动物的影响

  • Jacques等[67]结合暴露和影响数据评估微塑料对土壤生物风险的研究,得出一个可以肯定的结论,随着土壤中微塑料浓度的增加,对土壤生物群的潜在风险也会增加。Wang等[68]研究表明,蚯蚓能够直接摄入微塑料颗粒,且在人为高浓度微塑料土壤环境下,微塑料颗粒和氧化应激会对组织造成损伤。Kwak等[69]的报告描述了土壤无脊椎动物接触微塑料影响其精囊中精子束的排列,对精子造成有害影响,且蚯蚓(Eisenia andrei)的体腔细胞毒性试验结果显示,接触微塑料的体腔细胞内酯酶活性显著下降,体腔细胞的细胞活力受到抑制。 Lei等[70] 通过将线虫(Caenorhabditis elegans)暴露在(纳米)微塑料的悬浊液中发现,(纳米)微塑料对线虫的运动具有兴奋毒性,如加快身体弯曲和头部摆动的频率,且线虫在1 μm塑料颗粒暴露下显著降低了线虫 unc-17unc-47 的表达,并对胆碱能和 γ-氨基丁酸能神经元造成明显损伤。此外,Lei等[71]还发现,接触微塑料会降低线虫的Ca2+ 水平,但增加了线虫肠道中谷胱甘肽S-转移酶的表达,这表明接触微塑料对肠道损害的主要影响是氧化应激。Ju等[72]研究发现,微塑料对白符跳虫(Folsomia candida)有明显的毒性作用,可以改变白符跳虫的肠道微生物群落,其中沃尔巴克氏菌(Wolbachia)的减少可能影响了白符跳虫的营养供应和免疫保护,从而可能导致弹尾虫繁殖率的下降和死亡,并且类似的变化在老鼠[73]体内被观察到,这需要更深入的研究来证实。Lin等[74]在我国重庆市金佛山平原区进行田间试验,发现田间添加低密度PE导致了土壤动物群落组成丰度的减少和转移,特别是在高浓度水平(15g/m2)下。

  • 3.4 微塑料对植物的影响

  • 目前微塑料对植物的毒性作用机理尚不清楚,且在植物组织中很难区分不同类型的微塑料。但有研究证明植物可以吸收微塑料,Bandmann等[75]用荧光微球检测观察到纳米级、微米级微塑料可以穿过植物细胞膜和细胞壁屏障,植物的内吞作用有助于纳米级(<100nm)荧光PS微球进入烟草BY-2细胞内。Li等[76]研究发现,亚微米和微米大小的PS和聚甲基丙烯酸甲酯颗粒能直接从莴苣 (Lactuca sativa L.)和小麦(Triticum aestivum L.)侧根出现的裂纹穿透入2种植物的中柱,这是一种有效的吸收方式。Li等[77]研究发现,PS纳米塑料首先在黄瓜(Cucumis sativus L.)根系中积累,然后通过茎被运输到叶子、花和果实中。

  • 微塑料的植物毒性主要取决于其种类和浓度,如PE对玉米(Zea mays L.)无明显的毒性,而在10%(w/w)PLA土壤中,表现出较高的植物毒性,但0.1%和1%(w/w)PLA对玉米无显著影响或刺激生长[56]。Yang等[78]研究发现,土壤加入高密度PE和PLA会增加Zn在玉米根中的积累,同时减少了Zn在地上部的分配,影响了养分的有效性以及植物的吸收和转运。安菁等[79]研究发现,土壤微塑料残留量较低时,大豆[Glycine max(L.) Merr.]随生育期的延长可通过自身抗氧化系统减小胁迫影响;残留量较高时,则植株叶面积、株高、根系活力等各项生理生化指标均受到较大程度的影响。大量研究显示,土壤微塑料的存在会影响植物正常生长,王成伟等[80]研究指出,PS和邻苯二甲酸二丁酯复合污染会抑制生菜(Lactuca sativa L.)的光合作用和糖代谢,从而降低生菜的品质。 Kleunen等[81]发现用于人工运动草坪的微塑料三元乙丙橡胶在5%及以上浓度时,对草地植物长叶车前(Plantago lanceolata L.)存活和生长有强烈的负效应。Boots等[82]通过围隔试验评价了土壤的生物物理响应,当接触到纤维或PLA微塑料时,黑麦草(Lolium perenne L.)种子发芽率较低,而且随着PLA微塑料的加入,枝条高度也有所降低。由于植物生长状况与土壤理化性质和根际微生物关系密切,因此微塑料也可以通过影响土壤性质和微生物群落的结构和相关微生物活性的变化,从而间接影响植物的表现[11]

  • 3.5 小结

  • 上述研究表明,微塑料进入土壤后,土壤生态系统受到了不同程度与形式的影响。微塑料改变了原有生态环境,其对土壤生态系统影响的程度与微塑料的种类、粒径、浓度等相关。并且,微塑料可以被植物和动物吸收,可能随着食物链进入人体,对人体健康具有潜在危害[483]。目前,针对微塑料对土壤生态系统影响的研究还不够系统,且仍未建立一个统一识别和分离的标准。最后,实际土壤中的微塑料可与有机污染物、重金属、抗生素等不同污染物共同对土壤生态系统产生影响[5684]。因此,了解微塑料对土壤生态系统可能造成的影响还需要进一步有针对性的研究。

  • 4 展望

  • 微塑料概念的提出距今已有16年,关于微塑料在土壤环境中的研究仍处于起步阶段,而关于土壤微塑料的研究更是远远不足,这一领域中的各项技术及机制仍未有统一的标准。目前,全球范围内微塑料污染严重,微塑料研究与治理问题亟待解决。

  • (1)土壤中微塑料存在覆盖范围广,由于微塑料的特性与塑料使用量的增加,未来土壤中微塑料污染将持续加重,可以通过量化某一途径进入土壤的微塑料,以评估其对土壤中微塑料的贡献,针对性加强对塑料使用与回收的管控工作,并通过减少塑料的使用、更新塑料回收处理标准的方法,从源头减少微塑料的产生。

  • (2)由于土壤的复杂性,且微塑料具有不同尺寸、结构和颜色,需要推进土壤微塑料的分离与识别技术研究,建立统一的土壤微塑料分离与识别技术,为土壤微塑料的研究提供技术支撑。

  • (3)土壤中微塑料来源多样,以不同的途径影响生态系统,需进一步了解其环境归宿,探究其对土壤生态系统中土壤理化性质、微生物、植物、动物影响的作用机制以及评估其可能对人体健康产生的影响。目前,针对微塑料对土壤生态系统的研究大部分是在室内模拟环境下进行的,并缺乏长期作用的研究,未来需要增加室外土壤中微塑料污染影响机制的研究。

  • (4)有研究发现,微塑料在环境中可以被一些微生物降解[85-88]。使用微生物降解微塑料是一种很有前途、环境风险低的治理方法,但是目前相关降解技术还不成熟,需要进一步深入微塑料在土壤中的降解机制与筛选降解菌株的研究。

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