摘要: 微塑料（MPs）作為一種新型環(huán)境污染物已成為當(dāng)下的研究熱點(diǎn), 有關(guān)微塑料的人體健康風(fēng)險(xiǎn)和危害效應(yīng)機(jī)制研究受到了廣泛關(guān)注.微塑料不斷地從環(huán)境中遷移并在人體內(nèi)積累, 其對人群暴露的3個(gè)主要途徑為經(jīng)口攝入、呼吸吸入和皮膚接觸, 主要暴露介質(zhì)為食品、飲用水、灰塵和個(gè)人護(hù)理品.目前已在人體消化系統(tǒng)、呼吸系統(tǒng)、心血管系統(tǒng)和生殖系統(tǒng)的器官、體液及排泄物中檢出微塑料, 豐度范圍為0~1 206.94 n·g-1.現(xiàn)有的檢測分析技術(shù)具有不同的適用范圍、優(yōu)勢和不足, 針對實(shí)驗(yàn)過程中可能污染樣品的問題列舉了實(shí)驗(yàn)室質(zhì)量保證和質(zhì)量控制的操作方法.基于動(dòng)物實(shí)驗(yàn)、人體細(xì)胞和器官模型的研究闡述了微塑料對人體5大系統(tǒng)造成的潛在健康影響和作用機(jī)制, 進(jìn)入人體后, 微塑料可能通過誘發(fā)細(xì)胞毒性、線粒體毒性、DNA損傷和細(xì)胞膜損傷等效應(yīng)過程, 進(jìn)而在人體各系統(tǒng)中引發(fā)器官的局部炎癥、菌群失調(diào)和代謝紊亂等嚴(yán)重后果, 來危害各系統(tǒng)及相關(guān)器官的正常功能.最后, 提出了現(xiàn)有研究中普遍存在的不足, 可為未來微/納米塑料對人體健康影響的研究提供方向.

BAO Ya-bo1,2,WANG Cheng-chen1,2,PENG Wu-guang1,2,NONG Dai-qian1,2,XIANG Ping1,2    

Abstract: The effect of microplastics on the ecological environment and human health has become a topical issue, and research on the risks and harmful effects of MPs on human health in particular has attracted widespread attention. Due to the characteristics of small size, low degradability, and easy migration, MPs continuously migrate from the environment to the human body, and their main exposure pathways are oral ingestion, inhalation, and dermal contact, with the main exposure media being food, drinking water, dust, personal care products, etc. MPs have been detected in organs, fluids, and excreta of digestive, respiratory, cardiovascular, reproductive systems, etc. The abundance range of MPs in the human body is 0-1 206.94 particles per gram. After entering the human body, MPs can cause cytotoxicity, mitochondrial toxicity, DNA damage, cell membrane damage, and other effects on human cells and organs, leading to serious consequences such as local inflammation, ecological imbalance, metabolic disorders, etc., in various systems. Owing to their small specific surface area, they can also adsorb pollutants such as heavy metals, organic pollutants, antibiotics, pathogens, and harmful microorganisms, causing combined toxicity and immunotoxicity. In the end, we highlighted general deficiencies in existing studies and provided directions for future research on the influence of MPs on human health.

Key words:microplastics(MPs)    contaminants    exposure pathways    human accumulation    toxic effects    

微塑料（microplastics, MPs）指直徑 < 5 mm的塑料微粒, 是近年來受國內(nèi)外廣泛關(guān)注的一種新型污染物.自20世紀(jì)50年代大規(guī)模生產(chǎn)以來, 塑料被廣泛應(yīng)用于建筑、包裝、運(yùn)輸、個(gè)人護(hù)理產(chǎn)品和醫(yī)藥, 全球塑料產(chǎn)量在1950~2020年間由150 t增長到3.67億t, 其中2020年我國塑料產(chǎn)量高達(dá)1.05億t[1].據(jù)統(tǒng)計(jì), 2019年全球塑料制品回收利用率僅9%, 按傳統(tǒng)模式處理率69%（包括：填埋和焚燒）, 無人管理而滯留環(huán)境的部分占22%[2].塑料制品的濫用和不合理處置是MPs產(chǎn)生的主要原因[3].MPs根據(jù)成因可以分為原生微塑料和次生微塑料.原生微塑料指特地生產(chǎn)用于添加到個(gè)人護(hù)理用品和化妝品中的塑料微粒[4].次生微塑料指環(huán)境中原先較大的塑料制品在UV輻射、生物作用和磨損等作用下降解而形成的塑料微粒[5].隨著研究發(fā)展的需要, 將微塑料依據(jù)直徑大小進(jìn)一步細(xì)分為：大塑料顆粒（> 25 mm）、中塑料顆粒（5~25 mm）、微塑料顆粒（1 μm~5 mm）、亞微塑料顆粒（100 nm~1 μm）和納米塑料顆粒（< 100 nm）[6].

由于粒徑小、易遷移和降解等特性[7], 微/納米塑料（M/NPs）廣泛分布于全球海洋、淡水、土地和大氣生態(tài)系統(tǒng)中.近年來, 伊朗新鮮積雪[8]、青藏高原河流[9]、阿爾卑斯山冰川[10]、北極中央盆地地下水[11]和中國海底沉積物[12]中均檢測出M/NPs, 其潛在的生態(tài)風(fēng)險(xiǎn)受到了廣泛關(guān)注.M/NPs進(jìn)入生態(tài)系統(tǒng)后, 不僅會(huì)影響其生態(tài)系統(tǒng)服務(wù)功能, 同時(shí)對動(dòng)物、植物和微生物產(chǎn)生有害影響[13].近年來, 越來越多的研究發(fā)現(xiàn)M/NPs可以通過口攝入和呼吸吸入進(jìn)入人體, 由于M/NPs粒徑小且比表面積大, 能夠作為載體吸附其他有毒污染物（如：重金屬、持久有機(jī)污染物、抗生素、多環(huán)芳烴和多氯聯(lián)苯等）及有害病原體（如：致病細(xì)菌和真菌等）并將它們帶入人體內(nèi), 從而產(chǎn)生健康危害[3].此外, M/NPs在人體內(nèi)降解后, 有毒添加劑（如：增塑劑、合成抗氧化劑、阻燃劑、光穩(wěn)定劑和染色劑等）隨之浸出[14, 15], 無疑會(huì)加重其毒性.目前, 有關(guān)M/NPs的人群暴露及其健康危害機(jī)制的研究成為了當(dāng)下的研究熱點(diǎn).鑒于此, 本文總結(jié)了M/NPs的人群暴露途徑, 在不同組織器官的富集特征, 及暴露后對人體產(chǎn)生的健康效應(yīng)機(jī)制, 并提出了該領(lǐng)域現(xiàn)有研究的不足和未來可能的熱點(diǎn)方向.

1 微/納米塑料的人體暴露途徑

人體與外界環(huán)境時(shí)刻進(jìn)行著物質(zhì)交換（圖 1）, 攝入食物、呼吸空氣和皮膚接觸的過程伴隨著M/NPs暴露.有研究表明, 經(jīng)口攝入和呼吸吸入是M/NPs人體暴露主要的途徑, 雖然目前缺乏M/NPs穿透皮膚屏障被吸收的直接證據(jù), 但理論上直徑 < 100 nm的納米塑料（NPs）能夠穿透皮膚屏障被吸收[16, 17].

1.1 伴隨食物經(jīng)口攝入

研究人員在海產(chǎn)品、飲品、食鹽、一次性塑料餐具和果蔬中檢測到了M/NPs, 并指出經(jīng)口攝入是M/NPs最主要的暴露途徑.有研究表明, M/NPs能夠沿著食物鏈向更高營養(yǎng)級(jí)轉(zhuǎn)移, 最終隨著食物轉(zhuǎn)移到人的消化系統(tǒng)中.Nor等[18]建立了兒童和成人終生暴露模型, 估算出一個(gè)兒童或成人每天攝入M/NPs的數(shù)量的中位數(shù)分別為553個(gè)與883個(gè).Cox等[19]匯編了來自鹽、海鮮、蜂蜜、飲用水和糖的M/NPs污染數(shù)據(jù), 并結(jié)合飲食習(xí)慣估算出美國民眾每人每年對M/NPs的攝入量約3.9×104~5.2×104個(gè).近年來, 食物中M/NPs的污染成為人們關(guān)注的焦點(diǎn).

1.1.1 海產(chǎn)品M/NPs污染

已有研究證實(shí)了一些浮游動(dòng)物和濾食性動(dòng)物能夠直接攝入M/NPs.目前, 全球已累計(jì)在120多種具有重要漁業(yè)價(jià)值的物種中發(fā)現(xiàn)了M/NPs污染, 其中M/NPs在貝類、魚類、甲殼類和海藻等海產(chǎn)品中被大量檢出[20~22].據(jù)統(tǒng)計(jì), 消費(fèi)者每食用100 g貽貝將攝入70種M/NPs.此外, 海洋生物消化道和鰓中M/NPs的富集更為豐富, 食用完整的或不完全去除內(nèi)臟的海產(chǎn)品會(huì)增加M/NPs對人體的暴露量[23, 24].最近的一項(xiàng)來自韓國的研究也證實(shí), 其民眾每人每年通過食用4種常售雙殼貝類造成的M/NPs攝入量達(dá)212個(gè)[25].

1.1.2 飲用水和飲料M/NPs污染

M/NPs普遍存在于各類飲用水和飲料中.其中, 水源污染、處理過程中污染和自來水管管壁脫落是自來水被M/NPs污染的主要原因[26].Kosuth等[27]研究發(fā)現(xiàn)自來水中M/NPs檢出率高達(dá)81%, 平均豐度為5.45 n·L-1, 每人每年因自來水?dāng)z入量約為5 800個(gè).因具有易攜帶性、選擇多樣性和食品安全性等優(yōu)點(diǎn), 瓶裝水和飲料的消費(fèi)日益增長, 自1940~2015年, 法國民眾每人每年對瓶裝水的消費(fèi)量從6 L增長至140 L[28].瓶裝水和飲料中M/NPs的主要來源是塑料瓶蓋與包裝瓶.Kankanige等[29]對泰國市場常售的一次性塑料瓶裝水進(jìn)行分析, 結(jié)果表明M/NPs平均豐度為（140±19）n·L-1, 粒徑約6.5~20 μm, 其主要聚合物類型為聚乙烯（PE）、聚對苯二甲酸乙二醇酯（PET）、聚丙烯（PP）和聚酰胺（PA）.相比自來水, 飲用瓶裝水導(dǎo)致更高的M/NPs攝入, 若人群僅通過飲用瓶裝水而達(dá)到推薦飲水量, 則每人每年因此產(chǎn)生的M/NPs額外攝入量將高達(dá)9×104個(gè), 若僅飲用自來水, 這一數(shù)值將減少到4×103個(gè)[19].可見飲用水M/NPs污染已成為人類攝入M/NPs的重要來源之一, 建議減少飲用塑料包裝的水或飲料以有效降低M/NPs的攝入量和健康風(fēng)險(xiǎn).

1.1.3 食鹽M/NPs污染

食鹽能提供人體必需元素, 是人類長期的必需品, 然而被M/NPs污染的食鹽是一個(gè)慢性暴露源.商品鹽（包括：海鹽、井鹽、巖鹽和湖鹽等）被M/NPs污染的問題已在全球各國廣泛報(bào)告[30~32].據(jù)Lee等[33]研究證實(shí), 全球94%的鹽產(chǎn)品中含有M/NPs, 包括27種聚合物類型, 其中PET、PP和PE占絕大多數(shù).食鹽被M/NPs污染是多源的, 在采集、風(fēng)干、加工和運(yùn)輸?shù)冗^程中, 食鹽都可能被M/NPs污染.更有研究發(fā)現(xiàn), 海鹽樣本中M/NPs的豐度遠(yuǎn)高于巖鹽及湖鹽樣本[30], 這可能與食鹽產(chǎn)生的天然環(huán)境中M/NPs污染程度有關(guān).

1.1.4 水果蔬菜的M/NPs污染

2022年, Conti等[34]首次在食用水果（蘋果和梨）與蔬菜（胡蘿卜、花椰菜、生菜和土豆）中發(fā)現(xiàn)M/NPs.Dong等[35]研究發(fā)現(xiàn), 1 μm的聚苯乙烯微塑料（PS-MPs）能夠進(jìn)入胡蘿卜根并積累在細(xì)胞間隙中, 而0.2 μm的PS-MPs則能夠遷移到葉子上, 并且土壤-植物系統(tǒng)中M/NPs的遷移受到重金屬的影響.As（Ⅲ）能使得細(xì)胞壁變形以及PS-MPs攜帶負(fù)電荷的面積增加, 從而使更大直徑的PS-MPs得以進(jìn)入胡蘿卜細(xì)胞.此外, Liu等[36]還在食用生雞蛋中檢測出M/NPs, 蛋黃中M/NPs的平均數(shù)量高于蛋白, 蒸熟操作后的結(jié)果不變.雞蛋中微塑料可能來自雞體內(nèi), 或是包裝和運(yùn)輸過程[37].

1.1.5 塑料包裝、餐具和廚具的M/NPs污染

食品接觸到塑料包裝、一次性餐具和廚具而引發(fā)M/NPs污染的問題廣泛存在.Du等[38]對中國5個(gè)城市常用的外賣餐盒進(jìn)行研究, 發(fā)現(xiàn)所有餐盒中都存在M/NPs, 它們主要源自塑料餐盒內(nèi)壁脫落和灰塵沉降.高溫、機(jī)械應(yīng)力和長時(shí)間存放食品都能導(dǎo)致塑料餐具產(chǎn)生更多M/NPs.假設(shè)每人每日消耗4~5個(gè)一次性塑料水杯, 每人每年將因此攝入3.7×104~8.9×104個(gè)M/NPs[39].使用塑料奶瓶而導(dǎo)致配方奶粉受到M/NPs污染的問題值得注意, Li等[40]研究發(fā)現(xiàn), 聚丙烯（PP）奶瓶一次性釋放的M/NPs的豐度高達(dá)1.62×107 n·L-1, 這可能對嬰兒健康構(gòu)成風(fēng)險(xiǎn).此外, 不粘鍋涂層通常以聚四氟乙烯（PTFE）作為主要材料, 涂層破損能導(dǎo)致2.3×106個(gè)微粒脫落[41].

1.2 呼吸與皮膚接觸暴露

M/NPs在室內(nèi)外環(huán)境空氣中普遍存在, 其主要來源是合成紡織品的磨損與洗滌、合成橡膠輪胎及建材的磨損、灰塵的懸浮與擴(kuò)散、以及空氣中懸浮的M/NPs能夠直接地和持續(xù)地被吸入人體呼吸道及肺部[42, 43].M/NPs進(jìn)入上呼吸道后, 大部分能夠通過咳嗽、打噴嚏以及擤鼻涕等方式排出, 或隨黏液一起吞咽, 其余進(jìn)入肺部的M/NPs中大部分能通過吞噬作用和淋巴運(yùn)輸清除, 余下的則會(huì)積累在肺部[42].有研究者使用人體模型進(jìn)行空氣采樣, 估算出一個(gè)輕度活動(dòng)的男性每天能吸入272個(gè)M/NPs[44].

個(gè)人護(hù)理用品（包括：牙膏和潔面乳）、化妝品（眼影）、合成紡織品和灰塵是皮膚接觸M/NPs的主要源頭[42, 45].作為人體的物理屏障, 皮膚能夠防止環(huán)境微粒的滲透, 直徑 < 100 nm的微粒才能穿透橫紋肌角質(zhì)層[16], 因此普通的皮膚接觸難以使M/NPs進(jìn)入人體.有研究表明直徑 < 40 nm的金屬銀納米粒子可以穿透皮膚, 19 nm的氧化鋅納米粒子可以透過皮膚進(jìn)入循環(huán)系統(tǒng)[46].Vogt等[47]研究發(fā)現(xiàn), 當(dāng)毛鞘被拔出時(shí), 40 nm的納米顆?？梢源┩该疫M(jìn)入表皮細(xì)胞.可能與其他納米粒子一樣, 老化的皮膚、患傷處和毛孔處對NPs有更強(qiáng)的滲透能力[48].然而目前有關(guān)M/NPs皮膚接觸暴露的研究較少, 并且缺乏關(guān)于M/NPs穿透皮膚屏障和產(chǎn)生毒性效應(yīng)的直接證據(jù), 但不能排除M/NPs能夠穿越皮膚屏障并誘發(fā)氧化應(yīng)激、局部炎癥和異物反應(yīng)的推論.

2 微塑料在人體內(nèi)的富集情況與檢測分析技術(shù)2.1 微塑料在人體內(nèi)的富集狀況及影響因素

由于人體實(shí)驗(yàn)涉及到生命健康和人倫道德等問題, 目前關(guān)于M/NPs的人體富集證據(jù)較為匱乏, 有限的證據(jù)主要源于對人體體液、排泄物、人體器官廢棄物和尸體的檢測.現(xiàn)將目前為止在人體中檢測出M/NPs富集情況總結(jié)為表 1.

表 1 人體中微/納米塑料的富集情況Table 1 Accumulation of micro/nano-plastics in the human body

自2019年首次在人類糞便中檢測出M/NPs以來, 至今已在人體的消化系統(tǒng)、呼吸系統(tǒng)、心血管系統(tǒng)和生殖系統(tǒng)的器官、體液和排泄物中檢測出M/NPs, 這表明M/NPs在人體內(nèi)普遍存在.其中, 血液、血栓和隱靜脈血管中的檢測結(jié)果支撐了M/NPs能夠隨著血液在血管中遷移的假設(shè).此外, 在人類母乳、胎盤、胎糞和嬰兒糞便中檢測到M/NPs的存在, 發(fā)現(xiàn)糞便中出現(xiàn)的MPs隨著嬰兒母乳攝入量而增加, 說明嬰兒糞便中M/NPs的主要來源可能是受污染的母乳和奶粉等[62].胎糞是嬰兒在出生后的首次排泄物, 主要為母體內(nèi)由胎盤供給的營養(yǎng)物質(zhì)代謝而來, 證實(shí)了經(jīng)人類胎盤離體模型的M/NPs轉(zhuǎn)運(yùn), 在動(dòng)物實(shí)驗(yàn)中發(fā)現(xiàn)MPs能夠代際傳遞[64~67].以上結(jié)果提示了M/NPs通過母體傳遞到胎兒或新生兒體內(nèi)的可能性, 包括M/NPs可能會(huì)通過乳汁傳遞和胎盤轉(zhuǎn)運(yùn), 然而, 嬰兒胎糞與母體胎盤中的M/NPs物質(zhì)構(gòu)成存在差異, 提示了部分M/NPs可能源自母體宮內(nèi)暴露源[62].

有研究表明, M/NPs普遍在食品和人類消化道組織中的富集, 并且具有穿越人體細(xì)胞和組織屏障的能力, 以上證據(jù)支撐了M/NPs能夠從消化道內(nèi)轉(zhuǎn)移并積累到消化道組織中的推測, 這一過程可能受到多種因素影響, 包括M/NPs的尺寸、形狀、表面形態(tài)、聚合物類型、暴露途徑、暴露時(shí)間和暴露濃度、人體組織特異性和健康狀況.其中, 粒徑是影響M/NPs被細(xì)胞內(nèi)化的主要因素[68~71].較大粒徑的M/NPs可能無法穿透細(xì)胞屏障進(jìn)入細(xì)胞內(nèi), 但會(huì)對細(xì)胞膜造成物理損傷；在進(jìn)入細(xì)胞的M/NPs中, 稍大的顆粒主要通過吞噬作用進(jìn)入細(xì)胞中, 較小的微粒則通過胞飲作用、網(wǎng)格蛋白和小泡介導(dǎo)進(jìn)入細(xì)胞, 它們最終都會(huì)在細(xì)胞質(zhì)中積累[70].聚苯乙烯納米塑料（PS-NPs）比PS-MPs更容易進(jìn)入細(xì)胞, 并且細(xì)胞對M/NPs的攝取量與暴露時(shí)間成正比[72].此外, 人體疾病可能是驅(qū)動(dòng)M/NPs富集的關(guān)鍵因素之一.Cetin等[50]研究發(fā)現(xiàn), 正常人結(jié)腸組織中的M/NPs數(shù)量遠(yuǎn)低于直腸腺癌患者結(jié)腸腫瘤組織中M/NPs的數(shù)量.Horvatits等[51]研究發(fā)現(xiàn), 相比無潛在肝病患者, 肝硬化患者的肝組織中M/NPs豐度更高.Chen等[73]對肺組織中的M/NPs進(jìn)行檢測, 其中2/3的M/NPs存在于腫瘤組織中.但不能排除M/NPs可能是誘發(fā)疾病的原因, 它們的因果關(guān)系還需要進(jìn)一步深入研究.此外, 職業(yè)條件（包括：工作時(shí)長和工作環(huán)境等）和人群年齡也會(huì)影響M/NPs在呼吸系統(tǒng)中的積累量[73, 74].其中, 室內(nèi)工作人員鼻腔沖洗液中的M/NPs豐度高于快遞員, 這可能是由于室內(nèi)灰塵樣本中的M/NPs豐度比室外的灰塵樣本高而導(dǎo)致的.另外, 組織特異性是影響M/NPs富集的可能因素之一, 結(jié)腸作為營養(yǎng)物質(zhì)吸收的器官可能有更高的M/NPs滲透性, 同時(shí), 消化過程導(dǎo)致M/NPs進(jìn)一步碎裂和降解, 使得結(jié)腸能夠接觸到更高豐度和更小粒徑的M/NPs, 以上因素導(dǎo)致了結(jié)腸中M/NPs的積累量明顯高于其他器官.雖然M/NPs在人體內(nèi)的存在已經(jīng)被證實(shí), 但其在各系統(tǒng)中的積累、轉(zhuǎn)移、最終歸宿和影響因素仍然存在許多知識(shí)空白, 需要更多探索性和驗(yàn)證性的研究, 以為人體健康風(fēng)險(xiǎn)評(píng)估提供完整和可靠的數(shù)據(jù).

2.2 人體中M/NPs的樣本處理及檢測技術(shù)

根據(jù)表 1可知, 目前在人體富集的M/NPs的檢測分析研究中, 需要先后經(jīng)過取樣、預(yù)處理（包括：消解、過濾和分離）以及微塑料的表征.微塑料的表征技術(shù)是核心, 通常分為物理特性分析視覺檢測和化學(xué)特性檢測技術(shù).視覺觀察是通過直接使用人眼或者借助光學(xué)顯微鏡對M/NPs進(jìn)行大致分類和計(jì)數(shù)的檢測技術(shù).由表 1可知, 研究中使用到了光學(xué)顯微鏡（包括：體式顯微鏡、熒光顯微鏡和偏振光顯微鏡）, 主要用于物理特性檢測（包括：濾膜上M/NPs的物質(zhì)識(shí)別、計(jì)數(shù)、尺寸、形態(tài)和顏色）.然而, 觀察結(jié)果常受到實(shí)驗(yàn)人員主觀選擇、顯微鏡質(zhì)量以及M/NPs自身物理特性影響, 導(dǎo)致較大誤差的產(chǎn)生, 故不建議單獨(dú)使用[75, 76].

根據(jù)表 1可知, 先前的研究中主要采用的化學(xué)檢測技術(shù)為拉曼光譜法（Raman）、傅里葉變換紅外光譜法（FT-IR）、熱裂解-氣相色譜/質(zhì)譜聯(lián)用法（Pyr-GC-MS）和激光直接紅外光譜法（LD-IR）等技術(shù)對人體內(nèi)M/NPs的化學(xué)特性（包括：聚合物類型、化學(xué)鍵和官能團(tuán)等）進(jìn)行檢測, 現(xiàn)將人體內(nèi)M/NPs的化學(xué)特性檢測技術(shù)總結(jié)為表 2.

表 2 人體中微/納米塑料的主要檢測方法Table 2 Main detection methods for micro/nano-plastics in the human body

上述不同檢測分析方法在識(shí)別和量化M/NPs方面具有各自的優(yōu)劣.然而, 組合技術(shù)利用了技術(shù)之間相互補(bǔ)充的特點(diǎn), 彌補(bǔ)了技術(shù)單獨(dú)使用時(shí)的不足.例如, 微拉曼（μRaman）和微傅里葉（μFTIR）是現(xiàn)在主流的檢測分析方法, 它們分別為拉曼光譜法和傅里葉變換紅外光譜法與光學(xué)顯微鏡相融合的組合技術(shù), 能夠同時(shí)檢測到M/NPs的物理化學(xué)特性指標(biāo), 擴(kuò)大微粒的檢測范圍并降低漏檢率.

此外, 取樣和預(yù)處理過程中也存在許多不足之處.首先, 人體M/NPs取樣的非標(biāo)準(zhǔn)化會(huì)導(dǎo)致樣品存在被污染的風(fēng)險(xiǎn), 從而降低結(jié)果的準(zhǔn)確性.為了實(shí)驗(yàn)室質(zhì)量保證和質(zhì)量控制, 研究人員們采取一些措施, 例如：①減少塑料制品使用, 包括使用棉制實(shí)驗(yàn)服與手套、玻璃或金屬器皿盛裝樣品和金屬濾網(wǎng)過濾.②減少樣品、試劑和設(shè)備的污染, 包括取樣后盡快用純水或過氧化氫沖洗后迅速封閉保存, 所有試劑和設(shè)備用錫箔覆蓋, 用超純水和乙醇清潔器皿等.③建立“空白對照組”用以對實(shí)驗(yàn)過程中產(chǎn)生的M/NPs污染的樣本進(jìn)行校正.④在無窗和無風(fēng)的超凈工作臺(tái)操作實(shí)驗(yàn), 避免M/NPs因氣流再懸浮污染樣品.⑤每個(gè)樣品單獨(dú)處理, 避免相互污染.其次, 人體樣本中M/NPs的提取多采用化學(xué)消解法, 即使用酸性或堿性的化學(xué)溶液對樣品進(jìn)行消解, 旨在減少其他背景雜質(zhì)的干擾.然而, 化學(xué)消解效果受消解試劑類型、消解溫度和時(shí)間的影響, 不當(dāng)或過度消解則可能會(huì)破壞M/NPs聚合物宏觀結(jié)構(gòu)從而使檢測結(jié)果出現(xiàn)誤差.針對上述不足之處, 應(yīng)該根據(jù)適用條件和檢測目的選擇合適的技術(shù)進(jìn)行檢測分析, 改良并制定M/NPs取樣和提取的統(tǒng)一標(biāo)準(zhǔn), 鼓勵(lì)業(yè)界內(nèi)積極開發(fā)成本低以及檢測結(jié)果全面的檢測分析技術(shù), 以促進(jìn)該領(lǐng)域研究的發(fā)展.

3 微塑料暴露對人體健康影響的機(jī)制研究

M/NPs能穿越組織屏障轉(zhuǎn)移至血液, 隨后到達(dá)全身各系統(tǒng)并在其組織和體液中不斷積累, 最終產(chǎn)生毒性效應(yīng)[77].M/NPs進(jìn)入細(xì)胞后, 能引發(fā)多種毒性效應(yīng), 包括氧化應(yīng)激、細(xì)胞毒性和基因毒性, 具體表現(xiàn)為細(xì)胞死亡、線粒體毒性、細(xì)胞膜損傷、DNA損傷和染色體畸變等, 進(jìn)而在人體各系統(tǒng)中引發(fā)器官的局部炎癥、菌群失調(diào)以及代謝紊亂等嚴(yán)重后果, 增加了相關(guān)疾病的發(fā)病風(fēng)險(xiǎn), 甚至?xí)鹉[瘤和癌癥的發(fā)生（圖 2）.此外, 由于鼠類在一定程度上與人具有生理相關(guān)性, 常將鼠類用于研究M/NPs對有機(jī)體健康影響.然而動(dòng)物模型實(shí)驗(yàn)存在成本高、周期長、不易操作和有違倫理等問題, 研究人員也嘗試運(yùn)用人體細(xì)胞和體外器官模型來研究M/NPs對人體健康風(fēng)險(xiǎn).基于此, 下文綜述了M/NPs對人體各個(gè)系統(tǒng)的潛在健康影響及其內(nèi)在機(jī)制.

素材來源于https://www.freepik.com圖 2 攝入和吸入微/納米塑料對人類健康造成的潛在風(fēng)險(xiǎn)Fig. 2 Potential risks of ingestion and inhalation of micro/nano-plastics to human health

3.1 消化系統(tǒng)

M/NPs首先影響消化系統(tǒng).當(dāng)食物依次通過口腔、食道、胃和腸道時(shí), M/NPs會(huì)隨之遷移, 其中一部分被排出體外, 另一部分則在體內(nèi)積累, 以上M/NPs可能引發(fā)消化道炎癥、屏障通透性增強(qiáng)和微生物失調(diào)等.Zhang等[72]推測PS-MPs可能通過破壞人類結(jié)腸上皮細(xì)胞線粒體電子傳遞鏈（ETC）以誘導(dǎo)線粒體去極化, 從而導(dǎo)致早期細(xì)胞凋亡.Luo等[78]研究發(fā)現(xiàn)攝入PS-MPs能夠加重小鼠結(jié)腸炎癥, 具體表現(xiàn)為結(jié)腸長度縮短、炎癥加重、粘液分泌減少和結(jié)腸通透性增加.Fournier等[79]研究表明, M/NPs影響嬰兒腸道菌群種類組成, 減少有益菌群豐度、增加有害菌群豐度, 并且菌群變化幅度受到M/NPs的尺寸、豐度和種類的影響.Tong等[80]研究發(fā)現(xiàn), 幽門螺桿菌（H.pylori）在聚乙烯微塑料（PE-MPs）表面形成生物膜, 這加快了H.pylori在小鼠胃中的定居速度, 從而加劇胃部損傷和炎癥.此外, 隨著PS-MPs濃度和表面粗糙程度的增加, 人類結(jié)腸腺癌細(xì)胞（Caco-2細(xì)胞）的細(xì)胞膜完整性遭到破壞, 細(xì)胞存活率逐漸下降[81].小鼠攝入高濃度PE-MPs后出現(xiàn)明顯的腸道炎癥, 其與炎癥相關(guān)跨膜受體蛋白和轉(zhuǎn)錄因子表達(dá)也隨之升高[82].

肝臟作為人體內(nèi)最大的代謝器官, 影響著脂肪的消化分解和脂溶性維生素的吸收.M/NPs可能對肝臟產(chǎn)生多種毒性, 包括氧化應(yīng)激、細(xì)胞膜損傷、細(xì)胞纖維化、脂肪代謝混亂和能量代謝混亂[83~85].M/NPs通過誘導(dǎo)人類正常肝細(xì)胞（HL7702細(xì)胞）中細(xì)胞核DNA和mtDNA損傷, 以及激活cGAS/STING信號(hào)通路, 從而導(dǎo)致肝纖維化[83].斑馬魚經(jīng)過M/NPs長期暴露, 其脂肪代謝混亂, 體重下降, 并且其脂肪酸代謝相關(guān)的基因表達(dá)水平出現(xiàn)降低趨勢[86].此外, M/NPs的毒性受多種因素的影響, 包括M/NPs的物理化學(xué)特性、M/NPs與其他污染物之間的相互作用.Wang等[87]研究發(fā)現(xiàn), 人工胃液能增強(qiáng)PS-MPs對肝細(xì)胞的毒害, 包括肝細(xì)胞的形態(tài)學(xué)改變、細(xì)胞膜損傷和氧化應(yīng)激引起的細(xì)胞凋亡增加.Banerjee等[88]研究發(fā)現(xiàn), 較小的微粒更容易被人肝癌細(xì)胞（HepG2細(xì)胞）內(nèi)化, 相比羧基化或非功能化PS-M/NPs, 胺化PS-M/NPs對HepG2細(xì)胞毒性更大.此外, PS-MPs與雙酚A（BPA）的聯(lián)合暴露能干擾脂肪代謝、加劇肝毒性, 并且干擾與多種脂質(zhì)代謝過程相關(guān)的基因等, 導(dǎo)致脂肪變性[89].

3.2 呼吸系統(tǒng)

肺是呼吸系統(tǒng)最重要的器官, 目前關(guān)于M/NPs對呼吸系統(tǒng)影響的研究主要是基于肺細(xì)胞開展的.M/NPs能夠誘導(dǎo)肺細(xì)胞活性氧（ROS）增加和線粒體膜電位下降, 改變細(xì)胞正常結(jié)構(gòu), 從而提高急慢性呼吸系統(tǒng)疾病的發(fā)病風(fēng)險(xiǎn).Zhang等[90]研究發(fā)現(xiàn), 聚對苯二甲酸乙二醇酯納米塑料（PET-NPs）誘導(dǎo)肺癌人類肺泡細(xì)胞（A549細(xì)胞）發(fā)生氧化應(yīng)激和線粒體膜電位下降.Goodman等[91]研究發(fā)現(xiàn), PS-MPs能誘發(fā)A549細(xì)胞形態(tài)改變, 使其細(xì)胞質(zhì)突起增加和細(xì)胞接觸喪失, PS-MPs通過影響人正常肺支氣管上皮細(xì)胞（BEAS-2B細(xì)胞）間連接蛋白, 導(dǎo)致肺屏障功能障礙, 增加了慢性阻塞性肺疾病的風(fēng)險(xiǎn)[92].此外, M/NPs的尺寸影響其內(nèi)化速度和肺部的微生物調(diào)節(jié).相比20 nm和100 nm的PS-NPs, A549細(xì)胞對40 nm的PS-NPs的內(nèi)化速度更快.這表明M/NPs可能存在內(nèi)化速度相對較快的粒徑范圍[71].Zha等[93]研究發(fā)現(xiàn), MPs與NPs均可誘發(fā)小鼠鼻腔和肺部微生物菌群失調(diào), 但NPs比MPs對肺部微生物區(qū)系的影響更大.此外, 環(huán)境中M/NPs的豐度與暴露時(shí)間影響著肺部患病風(fēng)險(xiǎn).例如, 合成紡織業(yè)和植絨業(yè)的工人長時(shí)間接觸高豐度的M/NPs, 其患肺炎和慢性支氣管炎風(fēng)險(xiǎn)遠(yuǎn)高于普通人[94].

3.3 生殖系統(tǒng)

不孕不育率的持續(xù)增長促使人們關(guān)注污染物對生殖系統(tǒng)的影響.M/NPs可能會(huì)引發(fā)細(xì)胞氧化應(yīng)激、抗氧化活性降低和線粒體功能障礙, 進(jìn)而引發(fā)生殖系統(tǒng)能量代謝失衡、激素紊亂和性器官損傷, 最終影響生殖能力下降, 造成不孕不育.M/NPs造成的雄性生殖毒性包括：睪丸質(zhì)量下降、睪酮分泌減少、血睪屏障（BTB）遭受破壞和生精小管損傷, 從而導(dǎo)致生精功能障礙和精子畸形率上升, 以及精子活性和數(shù)量的下降[95~97].Jin等[98]研究證實(shí), < 10 μm的MPs能進(jìn)入睪丸細(xì)胞, 并在小鼠睪丸中積累.進(jìn)入睪丸后, PS-MPs通過Hippo信號(hào)通路誘導(dǎo)幼鼠睪丸發(fā)育障礙[99], 通過氧化應(yīng)激激活MAPK-Nrf2通路, 從而破壞大鼠BTB的完整性[97].此外, 常用的塑化劑鄰苯二甲酸鹽不僅會(huì)影響性激素分泌, 還能夠增加PS-MPs導(dǎo)致的睪丸轉(zhuǎn)錄組改變, 誘導(dǎo)氧化應(yīng)激[100].

M/NPs誘發(fā)的雌性生殖毒性包括卵巢毒性、發(fā)情期縮短和影響后代的發(fā)育與健康.其中, 卵巢毒性包括卵巢炎癥、卵泡數(shù)量減少、卵巢細(xì)胞纖維化及細(xì)胞凋亡和顆粒細(xì)胞脫落[101~103].此外, 由于孕期和嬰兒期是環(huán)境暴露的窗口期, 環(huán)境污染物容易影響胎兒的健康與發(fā)育.PS-NPs通過影響肌肉和脂質(zhì)的代謝延緩小鼠胎兒生長, 導(dǎo)致其體重下降[104].PS-NPs能在小鼠間存在代際傳遞現(xiàn)象, 并能在子代大腦中積累, 導(dǎo)致子代神經(jīng)干細(xì)胞功能、神經(jīng)細(xì)胞組成變化和神經(jīng)發(fā)育異常, 從而增加其神經(jīng)發(fā)育缺陷和大腦功能障礙的風(fēng)險(xiǎn)[105].胎盤的主要功能是將營養(yǎng)物質(zhì)從母體轉(zhuǎn)運(yùn)至胎兒, 提供膽固醇和類固醇激素以維持妊娠和胎兒發(fā)育.先前關(guān)于胎盤模型的研究表明, M/NPs的尺寸、表面特性、官能團(tuán)和蛋白冠的不同組成能夠影響胎盤對M/NPs的攝取和轉(zhuǎn)運(yùn)[66].人血白蛋白是提升M/NPs的轉(zhuǎn)運(yùn)的關(guān)鍵因素[106].此外, 一些塑料添加劑被視為內(nèi)分泌干擾物, 需關(guān)注妊娠期暴露塑料添加劑對相關(guān)激素的干擾, 及其與胎盤功能相關(guān)基因之間存在的潛在相關(guān)性[107].

3.4 免疫系統(tǒng)

M/NPs對免疫系統(tǒng)的毒性主要包括免疫毒性、提高有害微生物和病原體的感染能力.其中, 巨噬細(xì)胞和淋巴細(xì)胞是M/NPs免疫毒性的主要對象.食品包裝釋放的N/MPs能夠直接被小鼠巨噬細(xì)胞吸收和積累[108].PS-NPs進(jìn)入人類THP-1巨噬細(xì)胞后, 能誘導(dǎo)ROS增加, 導(dǎo)致核損傷與線粒體膜電位下降, 從而降低細(xì)胞生存力.其中, 由不同結(jié)構(gòu)和粒徑組成的PS-NPs混合物能產(chǎn)生更高的細(xì)胞毒性, 甚至改變THP-1巨噬細(xì)胞形態(tài)[109].?obano?lu等[110]發(fā)現(xiàn)PE-MPs對人外周血淋巴細(xì)胞產(chǎn)生基因毒性, 增加其微核（MN）、核質(zhì)橋（NPB）和核芽（NBUD）形成的頻率.此外, M/NPs可能通過干擾免疫相關(guān)的基因和蛋白質(zhì)影響免疫調(diào)節(jié).PE-MPs暴露增加了小鼠血液內(nèi)中性粒細(xì)胞數(shù)量及免疫球蛋白A（IgA）水平, 并改變脾臟內(nèi)的淋巴細(xì)胞亞群結(jié)構(gòu)[111].

受污染的M/NPs作為載體, 提高了病原體和有害微生物對人體的感染能力, 這對免疫系統(tǒng)健康造成了嚴(yán)重威脅.Wang等[112]研究發(fā)現(xiàn), 大量甲型流感病毒（IAV）能夠富集在PS-MPs上, 并通過內(nèi)吞作用進(jìn)入A549細(xì)胞中, 這促進(jìn)了IAV對A594細(xì)胞的感染.Kampf等[113]研究發(fā)現(xiàn), 冠狀病毒能連續(xù)9 d在塑料表面保持傳染性.紫外線輻射下老化的M/NPs對病毒有更強(qiáng)的吸附能力, 這能延長病毒存活期, 增加病毒傳染性[114].此外, M/NPs能夠在各種環(huán)境和生物之間傳遞抗生素抗性基因[115], 可能會(huì)增加有害微生物的抗生素耐藥性.

3.5 心血管系統(tǒng)

有研究提示M/NPs可能會(huì)導(dǎo)致血液毒性和血管毒性, 并受M/NPs自身的物理化學(xué)特性影響.其中, 血液毒性包括M/NPs引發(fā)溶血、血栓和凝血.Barshtein等[116]研究表明, PS-NPs引發(fā)溶血受微粒的尺寸和豐度影響, 但人血白蛋白是最關(guān)鍵的影響因素, 可以阻止溶血發(fā)生.Wu等[58]研究推斷, 環(huán)境微?？赡苁茄ㄐ纬傻暮诵? 初始血栓會(huì)持續(xù)吸引血液中的微粒, 以增大血栓的體積.Oslakovic等[117]研究發(fā)現(xiàn), 胺基改性NPs與凝血相關(guān)因子Ⅶ和Ⅸ與結(jié)合能夠減少凝血酶的形成.此外, M/NPs能夠產(chǎn)生血管毒性.100 nm的NPs能在人臍靜脈內(nèi)皮細(xì)胞的細(xì)胞質(zhì)中積累, 誘導(dǎo)自噬啟動(dòng)和自噬體形成, 這可能會(huì)引發(fā)細(xì)胞自噬過度和細(xì)胞壞死, 從而影響血管形成能力[68, 118].此外, M/NPs可能會(huì)導(dǎo)致心率異常和心臟功能受損.Chen等[119]研究發(fā)現(xiàn), 在水環(huán)境暴露PS-M/NPs后, 海洋小鳉胚胎的血紅蛋白和心臟發(fā)育相關(guān)基因表達(dá)受到影響.Pitt等[67]研究發(fā)現(xiàn), PS-NPs在斑馬魚中出現(xiàn)代際傳遞現(xiàn)象, 并在子代中觀察到心率過慢.Roshanzadeh等[120]研究發(fā)現(xiàn), 胺化羧酸鹽PS-NPs導(dǎo)致新生大鼠心肌細(xì)胞（NRVMs）收縮力降低, 影響方式隨時(shí)間而變化.前期, 由細(xì)胞內(nèi)Ca2+水平和電生理活動(dòng)的降低導(dǎo)致NRVMs收縮力降低；晚期則由于線粒體膜電位和細(xì)胞代謝的下降導(dǎo)致NRVMs收縮力進(jìn)一步下降.

4 展望

研究重點(diǎn)逐漸從最初探究M/NPs的環(huán)境分布狀況與生態(tài)環(huán)境影響, 轉(zhuǎn)移到評(píng)估M/NPs造成的人類健康的影響且研究成果頗多, 但目前仍存在許多知識(shí)空白：

（1）關(guān)于M/NPs人體暴露狀況的研究, 大多針對環(huán)境介質(zhì)進(jìn)行檢測分析, 關(guān)于綜合暴露源頭導(dǎo)致的暴露量評(píng)估極其匱乏.應(yīng)結(jié)合不同暴露途徑與暴露源, 以及地域、年齡、性別、職業(yè)和生活習(xí)慣等影響因素, 建立相關(guān)模型, 從而更為精確且全面地評(píng)估人體暴露量.

（2）以往研究的樣本量較少, 實(shí)驗(yàn)數(shù)據(jù)受個(gè)體差異與檢測方法影響較大.需要更多資源的支持以開展大規(guī)模的M/NPs人體富集狀況的檢測.

（3）小粒徑和高濃度下M/NPs的富集和毒性有所增加.但毒理實(shí)驗(yàn)多選用粒徑統(tǒng)一的PS微球作為暴露試劑.要考慮M/NPs在實(shí)際環(huán)境中的復(fù)雜性（如：尺寸、形狀、聚合物組成、表面形態(tài)和風(fēng)化程度等）.特別是M/NPs作為載體, 與其他環(huán)境污染物和有害微生物病原體之間存在相互作用及聯(lián)合毒性需要更多地關(guān)注.

（4）毒理研究集中于M/NPs高濃度急性暴露對人體健康的負(fù)面影響, 尚不清楚長期暴露的后果.然而實(shí)際環(huán)境狀況中暴露濃度低且M/NPs的生物積累和降解程度會(huì)隨著時(shí)間的推移而增加, 影響著M/NPs的生物毒性.因此, 基于低濃度和生命周期的M/NPs暴露對人體毒性的評(píng)估也是未來重要的研究方向.

5 結(jié)論

經(jīng)口攝入是環(huán)境中的M/NPs最主要的暴露渠道, 食物、水和空氣是最主要的環(huán)境介質(zhì), 應(yīng)重視.M/NPs在人體中的積累較為普遍, 但豐度較低, 除結(jié)直腸腺癌腫瘤組織外, 約（702.68±504.26）n·g-1 M/NPs突破組織屏障后隨著血液循環(huán)至全身各系統(tǒng), 粒徑較大的M/NPs雖然無法進(jìn)入細(xì)胞, 但會(huì)損壞細(xì)胞膜, 較小的M/NPs能夠進(jìn)入細(xì)胞內(nèi)并在細(xì)胞質(zhì)中積累.M/NPs毒性受到其尺寸、形狀、表面形態(tài)、聚合物類型、暴露途徑、暴露時(shí)間和暴露濃度的影響, 此外M/NPs在體內(nèi)降解中會(huì)釋放有毒塑料添加劑, 并且M/NPs能將環(huán)境中其他有害污染物、微生物和病原體帶入體內(nèi), 以上因素能夠在細(xì)胞層面誘發(fā)氧化應(yīng)激、細(xì)胞毒性、線粒體毒性和基因毒性等, 進(jìn)而導(dǎo)致各系統(tǒng)炎癥反應(yīng)、屏障受損、代謝紊亂、內(nèi)分泌紊亂以及菌群失調(diào), 增加了各系統(tǒng)相關(guān)疾病的發(fā)病風(fēng)險(xiǎn), 甚至?xí)鹉[瘤和癌癥的發(fā)生.然而, M/NPs對人體的毒害機(jī)制研究尚處于初步階段, 動(dòng)物和人對污染物的毒性反應(yīng)有所差異, 細(xì)胞和器官模型不能模擬真實(shí)的人體內(nèi)部狀況, 其實(shí)驗(yàn)結(jié)果用于評(píng)估M/NPs對人體健康風(fēng)險(xiǎn)存在不足之處.

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