全氟和多氟化合物替代品的研究進(jìn)展

周秀鵑，盛南，王建設(shè)，戴家銀

中國科學(xué)院動(dòng)物研究所，中國科學(xué)院動(dòng)物生態(tài)與保護(hù)生物學(xué)重點(diǎn)實(shí)驗(yàn)室，北京 100101

全氟和多氟化合物替代品的研究進(jìn)展

周秀鵑，盛南，王建設(shè)，戴家銀*

中國科學(xué)院動(dòng)物研究所，中國科學(xué)院動(dòng)物生態(tài)與保護(hù)生物學(xué)重點(diǎn)實(shí)驗(yàn)室，北京 100101

全氟和多氟化合物(per-and polyfluoroalkyl substances, PFASs)是一類新型持久性有機(jī)污染物(POPs)，廣泛應(yīng)用于工業(yè)和人類日常生活用品中。此類化合物具有高能量的C-F共價(jià)鍵，因此具有優(yōu)良的理化特性和生物穩(wěn)定性。由于存在持久性、生物累積性、長距離遷移以及毒性等問題，長鏈PFASs(C>7)已經(jīng)成為全世界關(guān)注的焦點(diǎn)之一，尋找能夠替代PFASs的新型化合物具有重要意義。本文介紹了幾種可能替代PFASs的新型氟化替代品，PFASs替代品在各類環(huán)境介質(zhì)中的分布、持久性、人體暴露及毒性等幾個(gè)方面進(jìn)行了綜述，特別對目前存在的問題及今后的研究方向進(jìn)行了討論和展望，以期為PFASs替代品的環(huán)境污染及風(fēng)險(xiǎn)評估提供參考。

全氟和多氟化合物；PFASs替代品；環(huán)境行為；人體暴露；毒性

Received18 June 2016accepted22 August 2016

Abstract: Per-and polyfluoroalkyl substances (PFASs) are an emerging kind of persistent organic pollutant currently widely used in industrial and daily life supplies. With high-energy C-F bonds, PFASs have excellent physical, chemical properties and biological stability and have drawn the attention of researchers all over the world due to their high persistence, bioaccumulation potential, toxicity and ubiquitous distribution in the environment, biota and humans. It is of vital importance to look for fluorinated alternatives to long-chain PFASs. This paper summarizes hot issues about PFASs alternatives, such as environmental distribution and behavior, persistence, human exposure and toxicity. The emphasis is laid on existing problems and future research perspectives so as to provide evidence for the investigation of existing problems and future research directions.

Keywords: per-and polyfluoroalkyl substances; PFASs alternatives; environmental behavior; human exposure; toxicity

全氟和多氟化合物(per-and polyfluoroalkyl substances, PFASs)是一類高度氟化的脂肪族物質(zhì)，即除官能團(tuán)中的氫原子外，碳骨架上的氫原子全部或部分被氟原子替代的人工合成有機(jī)化合物[1]。由于PFASs的理化特性極其特殊，包括較強(qiáng)穩(wěn)定性、疏水、疏油性等，被廣泛地應(yīng)用于地毯、皮革、紡織、包裝、滅火泡沫、洗發(fā)香波、地板打磨、電鍍等工業(yè)和民用領(lǐng)域。目前環(huán)境中存在的PFASs主要有全氟烷基羧酸(PFCAs)、全氟烷基磺酸(PFSAs)、全氟烷基磺酰胺(FOSAs)、氟化調(diào)聚醇(FTOHs)、全氟磷酸(膦酸)及其酯等，其中全氟辛烷羧酸(perfluorooctanoic acid, PFOA)和全氟辛烷磺酸(perfluorooctane sulfonic acid, PFOS)是目前最受關(guān)注和應(yīng)用最廣泛的2種典型全氟有機(jī)化合物。由于結(jié)構(gòu)中含有高能量的C-F化學(xué)鍵(C-F: 485.3 kJmol-1)，該類化合物普遍具有很高的穩(wěn)定性，難以水解、光解和被微生物降解，因此許多PFASs具有環(huán)境持久性及高生物累積性[2]。大量研究表明PFASs已在各種環(huán)境介質(zhì)和生物體中廣泛檢出，包括表層水[3-5]、污泥[6-7]、沉積物[8]、灰塵[9-10]、海洋生物[11-12]等，甚至人體中也檢出多種PFASs[13-15]。流行病學(xué)研究發(fā)現(xiàn)PFASs的人體暴露與一些生化和生理指標(biāo)的改變存在一定的正相關(guān)，包括腎癌和睪丸癌[16]、潰瘍性結(jié)腸炎[17]、孕期高血壓[18]、高膽固醇[19-20]、甲狀腺機(jī)能減退[21-22]、免疫系統(tǒng)疾病[23-24]、胎兒生長遲緩[25-27]、妊娠期糖尿病[28]等。此外，毒理學(xué)研究也發(fā)現(xiàn)PFASs具有肝毒性[29]、神經(jīng)毒性[30]、生殖發(fā)育毒性[29,31]、免疫毒性[29]、致癌性[32]、干擾脂肪代謝[33]以及內(nèi)分泌干擾效應(yīng)[34-35]等多種毒性。

由于PFASs具有持久性、累積性、長距離遷移以及高毒性等特性，嚴(yán)重地威脅了生態(tài)環(huán)境和人體健康，2001年國際社會共同簽署了《關(guān)于持久性有機(jī)污染物(Persistent Organic Pollutants，簡稱POPs)的斯德哥爾摩公約》，開啟了保護(hù)環(huán)境和人類健康免受有毒污染物危害的全球行動(dòng)。3M公司于2002年停止生產(chǎn)PFOS及其相關(guān)產(chǎn)品。2009年5月9日聯(lián)合國環(huán)境規(guī)劃署正式將PFOS及全氟辛基磺酰氟(PASF)等列為新的持久性有機(jī)污染物，同意減少并最終禁止使用該類物質(zhì)。最近，歐洲化學(xué)品管理局(ECHA)公布提案，建議將PFOA、全氟辛酸銨(APFO)以及C11～C14 PFCAs等化學(xué)品列為高度關(guān)注物質(zhì)[36]。

長鏈PFASs的安全問題已經(jīng)引發(fā)全球研發(fā)者和使用者的高度關(guān)注。淘汰部分長鏈PFASs，雖然減少了含氟聚合物生產(chǎn)過程中某些長鏈PFASs的使用量及排放量，但仍然無法從根本上解決長鏈PFASs的環(huán)境問題。為了適應(yīng)全球化的發(fā)展，保護(hù)自身環(huán)境，研發(fā)無潛在生物蓄積性、低毒性的高性能化合物已迫在眉睫，尋找和研發(fā)新的PFASs替代品成為近年來科研工作者研究的熱點(diǎn)之一。本文在2篇已有綜述的基礎(chǔ)上[37-38]，概述了幾種可能替代PFASs的新型化合物及其持久性、人體暴露及毒性等，對目前存在的問題及今后的研究方向進(jìn)行了討論和展望，以期為PFASs替代品的環(huán)境污染及風(fēng)險(xiǎn)評估提供參考。

1 長鏈PFASs替代品分類(The classification of long chain PFASs alternatives)

美國環(huán)境保護(hù)署(USEPA)提出禁用PFOA以后，其國內(nèi)外就開展了PFASs替代品研究并取得了實(shí)質(zhì)進(jìn)展。迄今為止，3M、大金、杜邦、旭硝子、阿科瑪和蘇威在內(nèi)的國際氟化工生產(chǎn)商已經(jīng)向USEPA上報(bào)了50余種PFASs替代品以待評估。如3M公司研發(fā)的PFOS替代品全氟丁基磺酸(PFBS)無明顯生物積累性，短時(shí)間內(nèi)可隨人體新陳代謝排出體外。由杜邦等公司利用調(diào)聚反應(yīng)生產(chǎn)的全氟烷基C6基產(chǎn)品，由于沒有C8基成分，沒有PFOS及其衍生物，也不產(chǎn)生PFOA。這些調(diào)聚物基含氟表面活性劑很可能降解為C6F13CH2CH2SO3H(6:2 FTSA)或C6F13CH2CH2COOH(6:2 FTCA)，而不是PFOS或PFOA，其毒性較C8小。國內(nèi)外針對PFASs替代品的研發(fā)一般分為2類：(1)使用C4、C6結(jié)構(gòu)的短鏈全氟烷基羧酸或磺酸鹽，如PFBA、PFHxA、PFBS。(2)含功能官能團(tuán)的全氟聚醚(PFPEs)，尤其是全氟聚醚羧酸和磺酸(PFESAs和PFECAs)，如6:2 FTCA、GenX、F-53B、6:2 FTSA。各化合物的結(jié)構(gòu)和名稱如表1所示。

2 PFASs替代品的環(huán)境含量以及應(yīng)用(The content, and application of PFASs alternative in environment)

一些研究表明作為C8全氟化合物替代物的C4全氟化合物在環(huán)境中的濃度不斷升高。Zhou等[39]在武漢湯遜湖氟化學(xué)工廠附近的水樣檢測到高濃度的PFBA和PFBS等短鏈全氟化合物，其濃度分別為3 660 ngL-1、4 770 ngL-1。6:2 FTSA作為PFOS的一種替代物，近年來被越來越多地使用在裝飾性電鍍行業(yè)和泡沫滅火器的生產(chǎn)過程中，如杜邦公司以6:2 FTSA合成了Forafac?1176。此外，6:2 FTSA還是Capstone?FS-17的主要成分[40]。最近在水體[41-44]、污泥[42,45-46]、消防基地[47]、城市垃圾填埋場滲濾液[48]等中都發(fā)現(xiàn)了6:2 FTSA。在我國，PFOS的替代物F-53B作為霧抑制劑廣泛地應(yīng)用于鍍鉻工業(yè)。Wang等[49]在溫州一個(gè)鍍鉻工業(yè)的廢水處理廠的進(jìn)水、出水中檢測到了高濃度的F-53B。由于污水處理廠不能夠有效去除該類物質(zhì)，在污水處理廠排放的地表水中也可以檢測到高濃度的F-53B。最近一些研究發(fā)現(xiàn)在污泥中也檢測到F-53B。據(jù)統(tǒng)計(jì)，F(xiàn)-53B年產(chǎn)量高達(dá)10多噸，其銷售保持逐年穩(wěn)步增長的態(tài)勢。由于全球禁止使用PFOS，F(xiàn)-53B在未來可能會有更大的市場份額[50-51]。在歐洲，PFOA替代物GenX作為加工助劑廣泛應(yīng)用于氟聚樹脂制造業(yè)，年產(chǎn)量高達(dá)10～100噸[50]。此外，在中國含氟乳化劑用6:2 FTCA替代了PFOA。目前在水體、污泥等介質(zhì)中均已檢測到PFASs替代物的存在(表2)。

表1 全氟和多氟化合物(PFASs)及其替代品Table 1 Per- and polyfluoroalkyl substances (PFASs) and PFASs alternatives

3 生物及人體暴露水平(The exposure of PFASs alternatives in the human and organisms)

自2002年3M公司終止全氟辛烷磺酰氟(POSF)的生產(chǎn)和PFOS正式進(jìn)入POPs名單以來，PFASs在環(huán)境中的濃度雖然有所下降，但是PFASs替代物在生物體不斷檢出。一項(xiàng)研究表明，在東格陵蘭島海洋哺乳動(dòng)物環(huán)海豹、北極熊、虎鯨中發(fā)現(xiàn)了高濃度F-53B[53]。Shi等[54]在小清河和湯遜湖中鯽魚血清、腎、性腺、肝臟以及心臟中檢出了F-53B。同時(shí)Shi等[55]研究發(fā)現(xiàn)食魚偏好者、鍍鉻工人以及普通人群尿液和血清也存在F-53B。另一項(xiàng)對6:2 FTSA的檢測發(fā)現(xiàn)，6:2 FTSA也存在于生物以及人體中(表3)。

暴露途徑研究是準(zhǔn)確認(rèn)識污染物健康效應(yīng)的一個(gè)重要前提。Shi等[55]研究認(rèn)為灰塵/空氣、飲用水和食物可能是PFASs替代物人體暴露的重要途徑。偏好食魚的人群血清中F-53B濃度中值是普通人的20倍，說明淡水魚可能是人體暴露的重要途徑。鍍鉻工人血清中濃度也遠(yuǎn)遠(yuǎn)超過普通人，可能通過灰塵/空氣、皮膚接觸等暴露途徑。最近一項(xiàng)研究也發(fā)現(xiàn)，通過羅納河的沉積物暴露，鉤蝦體內(nèi)發(fā)現(xiàn)了6:2 FTSA，因此食物和呼吸可能是鉤蝦暴露的途徑[42]。

高度重視PFASs替代物的人體累積和清除是科學(xué)研究的一個(gè)熱點(diǎn)。與普通人群不同的是，一些特殊人群可能面臨比普通人群更高或者不同特征的PFASs替代品暴露，這種情況值得高度關(guān)注。一項(xiàng)對食魚偏好者、鍍鉻工人、以及普通人體血液和尿液中血清中的F-53B和PFOS濃度清除半衰期的研究表明，人體對F-53B的血液清除較慢，半衰期較長，其半衰期的中值分別為15.3和6.7年，F(xiàn)-53B的半衰期顯著長于PFOS[55]。

表2 PFASs替代品在環(huán)境中的檢出量Table 2 The detection of PFASs alternatives in the environment

4 PFASs替代品的潛在影響(The potential impact of PFASs alternatives)

最近一些研究表明短鏈全氟替代物生物富集因子較低，基本沒有生物富集趨勢[42,60]。但仍有研究學(xué)者提出部分PFASs替代物具有持久性、生物累積性以及毒性等問題。最近研究發(fā)現(xiàn)有些替代物的降解產(chǎn)物仍然具有毒性。如全氟丁基磺酰氟(PBSF)和6:2全氟調(diào)聚物最終降解為短鏈PFASs和其他物質(zhì)，如高毒性的碳酰氟(COF2)[61]。因此，PFASs替代物對環(huán)境和生態(tài)影響仍然值得關(guān)注。關(guān)于PFASs替代物的特性見表4。

表3 PFASs替代品在生物及人體組織中的檢出量Table 3 The detection of PFASs alternatives in the human and organisms

表4 短鏈PFASs和全氟聚醚(PFPEs)的理化性質(zhì)Table 4 The physical and chemical properties of short chain PFASs and perfluoropolyether (PFPEs)

4.1 持久性

4.2 生物累積性

生物累積性是衡量污染物是否屬于POPs的一個(gè)極其重要依據(jù)，也是近年來PFASs研究的一個(gè)重要內(nèi)容。與長鏈類似物相比，短鏈全氟化合物在生物和人體內(nèi)基本沒有生物累積趨勢[60]，但在植物的葉、莖、果實(shí)中很易積累[69-70]。最近研究發(fā)現(xiàn)，6:2 FTSA對虹鱒魚的生物富集系數(shù)< 40，同時(shí)研究發(fā)現(xiàn)虹鱒魚對6:2 FTSA的食物吸收效率、生長半衰期以及食物放大因子分別為0.435、23.1和0.295，因此虹鱒魚對6:2 FTSA的積累性很低[71]。Shi等[55]對不同人群血液及尿液中的F-53B的消除動(dòng)力學(xué)進(jìn)行了分析，F(xiàn)-53B的血液清除半衰期小于PFOS的清除半衰期，但是由于物種的敏感度、灌喂的劑量方法以及實(shí)驗(yàn)技術(shù)等原因，關(guān)于PFECAs和PFESAs的生物累積性還需要更多的驗(yàn)證。

4.3 長距離遷移

許多PFASs具有POPs的遠(yuǎn)距離遷移特性，與長鏈類似物相比，具有較高水溶性、低吸附性的短鏈PFASs更易在環(huán)境中遷移[72-73]。PFECAs和PFESAs不僅與PFCAs和PFSAs結(jié)構(gòu)類似，而且具有持久性，因此在水中也可能具有長距離運(yùn)輸?shù)臐摿74]。到目前為止，還未在偏遠(yuǎn)地區(qū)發(fā)現(xiàn)PFECAs和PFESAs，可能由于(1)有些PFECAs和PFESAs近期才開始使用，使用量少并且排放量少；(2)PFECAs和PFESAs可能以前體形式存在；(3)排放和遷移到偏遠(yuǎn)地區(qū)形成污染物之間有一定的時(shí)間間隔；(4)沒有靈敏的檢測方法以及檢測標(biāo)準(zhǔn)。

4.4 毒性

高度重視人體健康效應(yīng)研究是PFASs環(huán)境研究的一個(gè)前沿和重點(diǎn)領(lǐng)域。研究表明，與長鏈類似物相比，大多數(shù)的短鏈PFASs替代品對人體和環(huán)境中生物沒有明顯的毒性效應(yīng)[75-76]。在對水生生物的急性和慢性毒性暴露研究發(fā)現(xiàn)，6:2 FTSA對水生生物幾乎沒有毒性。如虹鱒魚96 h半數(shù)效應(yīng)濃度(96 h-LC50)> 107 mgL-1，大型蚤48 h的半數(shù)效應(yīng)濃度(48 h-EC50) > 112 mgL-1[72]。Hoke等[77]研究發(fā)現(xiàn)6:2 FTCA對水蚤的48 h-LC50> 97.5 mgL-1，海藻72 h-EC50= 47.9 mgL-1，搖蚊10 d-LC50= 75.2 mgL-1，浮萍7 d-EC50= 1.3 mgL-1。根據(jù)美國環(huán)保署毒品管理?xiàng)l例(USEPA TSCA)中水生動(dòng)物毒性評估條例的規(guī)定，急性毒性的參考值為1 mgL-1< EC/LC50< 100 mgL-1，因此，6:2 FTCA對水生無脊椎動(dòng)物毒性并不大。Mitchell等[78]也研究發(fā)現(xiàn)6:2 FTCA對淡水無脊椎動(dòng)物的毒性不大。如6:2 FTCA抑制小球藻生長的EC50= 26.2 mgL-1，對月牙藻的生長抑制EC50>53 mgL-1，而對端足蟲10 d的死亡LC50= 33.1 mgL-1。Phillips等[79]也發(fā)現(xiàn)6:2 FTCA抑制搖蚊生長的EC50= 63 mgL-1。Wang等[38]研究發(fā)現(xiàn)F-53B對斑馬魚毒性與PFOS類似，其96 h-LC50分別為15.5 mgL-1和17 mgL-1。GenX不僅對皮膚、眼睛造成刺激，在低劑量濃度連續(xù)暴露(≤ 10 mgkg-1d-1)還可能引起肝癌[70]。關(guān)于PFASs替代品的毒性還需要更多的實(shí)驗(yàn)驗(yàn)證。

表5 PFASs替代品的降解性實(shí)驗(yàn)Table 5 The degradability of PFASs alternatives

5 PFASs替代品研究存在的問題與展望(The existing problems and perspectives of PFASs alternatives)

PFASs替代品對人和環(huán)境是否安全？最近一些研究發(fā)現(xiàn)結(jié)構(gòu)類似物的替換并不能真正解決問題，相反會出現(xiàn)“鎖定”問題[38]。為了解決這一問題，PFASs替代品的信息如特性、產(chǎn)量、用量、排放量以及毒性需要公開。然而，目前由于新型化合物研發(fā)費(fèi)用高、時(shí)間長以及公司為了增加競爭力，PFASs替代品信息并未完全公開。同時(shí)對PFASs替代品的環(huán)境行為及生態(tài)毒理效應(yīng)方面的研究也尚未系統(tǒng)開展。今后應(yīng)該開展如下研究：鼓勵(lì)公司公開替代品的信息，加強(qiáng)各部門之間的交流；注重PFASs替代品在各環(huán)境介質(zhì)以及人體內(nèi)的監(jiān)測，加快對PFASs替代品在各種環(huán)境介質(zhì)降解機(jī)制的研究；完善新的替代品在環(huán)境介質(zhì)和生物中的分析方法，以使分析數(shù)據(jù)具有可比性；系統(tǒng)地進(jìn)行全氟替代品的來源、分布、遷移轉(zhuǎn)化等研究；重視暴露途徑、生物有效性的研究，并與風(fēng)險(xiǎn)評估相結(jié)合；開展低劑量、長期、慢性毒性和復(fù)合毒性研究，整合多種組學(xué)從分子、基因等水平研究其毒性機(jī)制，這些研究結(jié)果為研發(fā)新的無潛在生物蓄積性、無毒性的高性能化合物提供技術(shù)支撐。

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◆

TheCurrentResearchStatusofSeveralKindsofFluorinatedAlternatives

Zhou Xiujuan, Sheng Nan, Wang Jianshe, Dai Jiayin*

Institute of Zoology, Chinese Academy of Sciences, Chinese Academy of Sciences Key Laboratory of Animal Ecology and Conservation Biology, Beijing 100101, China

10.7524/AJE.1673-5897.20160618001

2016-06-18錄用日期2016-08-22

1673-5897(2017)3-003-10

X171.5

A

戴家銀(1965—)，男，博士，研究員，主要從事持久性污染物的生態(tài)毒理學(xué)研究工作，發(fā)表學(xué)術(shù)論文90余篇。

國家自然科學(xué)基金(31320103915，21477126)

周秀鵑(1990-)，女，碩士研究生，研究方向?yàn)樯鷳B(tài)毒理學(xué)，E-mail: zhouxiujuan@ioz.ac.cn；

*通訊作者(Corresponding author)， E-mail: daijy@ioz.ac.cn

周秀鵑, 盛南, 王建設(shè), 等. 全氟和多氟化合物替代品的研究進(jìn)展[J]. 生態(tài)毒理學(xué)報(bào)，2017, 12(3): 3-12

Zhou X J, Sheng N, Wang J S, et al. The current research status of several kinds of fluorinated alternatives [J]. Asian Journal of Ecotoxicology, 2017, 12(3): 3-12 (in Chinese)