地表水中全氟及多氟烷基化合物（PFASs）的污染现状研究进展

黄柳青; 王雯冉; 张浴曈; 徐翊宸; 王新皓; 俞学如; 陈森; 谷成; 陈张浩

doi:10.7524/j.issn.0254-6108.2022090901

地表水中全氟及多氟烷基化合物（PFASs）的污染现状研究进展

1.
南京大学环境学院，污染控制与资源化国家重点实验室，南京，210023
2.
南京市生态环境保护科学研究院，南京，210013

通讯作者: E-mail：zhchen@nju.edu.cn

基金项目:
中国博士后科学基金（2021M701662）和国家自然科学基金（21777066）资助.

Research progress on the pollution status of per-and polyfluoroalkyl substances (PFASs) in surface water: A review

1.
School of the Environment, State Key Laboratory of Pollution Control and Resource Reuse, Nanjing University, Nanjing, 210023, China
2.
Nanjing Municipal Academy of Ecological and Environment Protection Science, Nanjing, 210013, China

Corresponding author: CHEN Zhanghao, zhchen@nju.edu.cn

Fund Project: the China Postdoctoral Science Foundation (2021M701662) and National Science Foundation of China (21777066).

摘要: 近年来，全氟及多氟烷基化合物（per- and polyfluoroalkyl substances，PFASs）的大量生产使用，使得其在自然水体中的浓度日益升高. 由于PFASs的生物毒性及强稳定性，环境中的PFASs严重威胁到生态环境及人类健康. 目前，多个国家及相关国际组织开始对地表水中的PFASs展开检测，但目前的监测基本属于点源监测，大范围、长时间维度的监测依然缺乏，从而无法准确揭示PFASs的时空赋存特征. 本文概述了PFASs在地表水中的赋存水平，同时阐述了地表水环境中PFASs的水平分布和垂直分布特征，并揭示了地表水中PFASs污染水平与组成的时间变化规律，总结了影响PFASs污染的主要因素，对后续PFASs监测提出了建议，以期为准确评估水环境中PFASs的污染状况提供依据.
- 全氟及多氟烷基化合物 /
- 地表水 /
- 污染特征 /
- 时空差异性.
Abstract: Recently, the mass production and usage of per- and polyfluoroalkyl substances (PFASs) have caused the serious PFASs pollution in natural water. Due to the biological toxicity and the strong persistence, PFASs pollution is threating the ecological environment and human health. Nowadays, many countries and international organizations have begun to monitor the PFASs pollution in surface water. However, the current monitoring only focus on the point source, and there still lacking the large-scale and long-term monitoring. Therefore, it is impossible to accurately reveal the spatiotemporal characteristics of PFASs pollution. This study summarizes the occurrence level of PFASs in surface water, and expounding the distribution characteristics of PFASs in the surface water. Moreover, the temporal variation law of PFASs pollution in surface water was revealed, and some environmental factors were also discussed. Finally, the follow-up suggestions on PFASs monitoring are proposed, providing a basis for accurately assessing the pollution status of PFASs in the environment.
- per- and polyfluoroalkyl substances (PFASs) /
- surface water /
- pollution characteristics /
- spatial and temporal differences

锑是元素周期表第五周期中的一种类金属元素，其在环境中广泛存在。锑及其化合物会引起肝脏、皮肤、呼吸系统和心血管系统疾病^[1-2]，已被美国环境保护署(USEPA)^[3]及欧盟^[4]列为优先控制污染物。此外，国际癌症研究机构(IARC)认为三氧化二锑可能对人类有致癌作用^[5]。随着锑开采和应用相关的人为活动（例如采矿、冶炼矿石、燃烧煤炭、废弹药以及各类产品(如阻燃剂、合金、半导体、塑料)的生产使用）干扰加剧，锑污染日益严重^[6-10]。中国拥有丰富的锑资源，是世界上最大的锑生产国，约占全球锑总产量的90%^[11]，在全球锑排放中也扮演着重要角色。近些年来，锑污染事件在中国时有发生，对人们的健康安全造成了极大的威胁^[12]。

受锑污染的水体中锑浓度可高达几千到几万微克每升^[13]。水环境中的锑可被动植物富集，继而通过食物链在人体内积累，危害人类健康^[14]。水产品是居民，尤其沿海城市居民日常膳食的重要组成部分，现阶段有关中国水产品中的锑研究仍十分有限，仅对烟台海产品和湖南水产品中锑有报道^[15-19]。

为更全面地了解中国沿海城市水产品中锑的赋存特征及其食用风险，本研究对中国8个典型沿海城市(盐城市、杭州市、舟山市、宁波市、台州市、温州市、福州市、深圳市)市售水产品中锑含量进行了检测，基于每日摄入评估量(EDI)及目标危害系数(THQ)对通过食用水产品摄入锑引起的潜在健康风险进行了评估，并根据各类水产品对THQ的贡献为中国沿海城市居民提供了水产品消费建议。

1. 材料与方法（Materials and methods）

1.1 样品采集和预处理

2019年2月至2020年5月，从中国8个典型沿海城市的当地菜市场共采集了124个水产品样品（盐城市：鱼类10个，贝类10个，虾1个；杭州市：鱼类16个，贝类7个，虾1个；舟山市：鱼类4个，贝类10个，虾1个；宁波市：鱼类4个，贝类7个，虾1个；台州市：鱼类2个，贝类4个，虾1个；温州市：鱼类4个，贝类8个，虾1个；福州市：鱼类6个，贝类12个，虾1个；深圳市：鱼类4个，贝类8个，虾1个）。针对每一个鱼类或贝类及虾类样品，采购1—3条或1.5 kg左右的量。采集的水产品运送至实验室后，测量样品长度，对于每个采样点的每一种虾类及贝类样品，随机各取8个进行长度测量，取平均值。用纯水清洗去除水产品表面泥沙等杂质，沥干后取贝类的可食用部分、鱼肉或虾肉，经冷冻干燥后，用研磨机研磨混匀，储存于−20℃冰箱。冷冻干燥前后称量样品重量以计算样品水分。样品脂肪含量根据中国食品安全国家标准（GB5009.6—2016）食品中脂肪的测定方法^[20]进行测定。对部分鱼类的其他部位(肝脏、鱼鳃、鱼皮、鱼籽)进行同样处理，用于锑在鱼体内的累积分布特征研究。

1.2 分析方法

根据中国食品安全国家标准（GB5009.137—2016）食品中锑的测定方法^[21]进行水产品中锑的测定。具体步骤：称取0.2—0.5 g冷干样品于微波消解罐中，加入5 mL硝酸、1 mL过氧化氢后进行微波消解。冷却后，加入20 mL水，加热赶酸至0.5—1 mL，将消化液转移至10 mL容量瓶中，用纯水定容至刻度。随后，取5 mL消化液，加入1 mL盐酸(30%，V/V)和1 mL预还原剂(10% (M/V)硫脲+10% (M/V)抗坏血酸)，稀释定容至10 mL。静置30 min后使用原子荧光光谱仪(AFS-9750，北京海光仪器有限公司)检测。

1.3 质量保证与质量控制

国家标准物质，扇贝成分分析标准物质(GBW10024)，购于中国计量科学研究院，用于确保检测方法的准确性。通过上述分析方法测定的扇贝标准物质中锑含量为(16.1±1.32)ng·g⁻¹，接近其参考值14 ng·g⁻¹。另外对样品进行加标回收实验，100—200 ng·g⁻¹加标水平下，锑的加标回收率在85%—98%范围内。水产品中锑的检出限（以3倍信噪比计）为0.13 ng·g⁻¹。在每批样品分析过程中，均增设了国家标准物质、平行样、加标回收及对照空白分析。所有数据均扣除空白。所有样品测定值的相对标准偏差值（RSD_{n = 3}）均小于10%。

1.4 健康风险评价

为评估通过食用水产品摄入锑对人体健康产生的潜在风险，对每日摄入评估量(Estimated daily intake EDI, μg·kg⁻¹·d⁻¹)进行了计算，计算公式如式(1):

$\mathrm{E}\mathrm{D}\mathrm{I}=\sum (C\times \mathrm{I}\mathrm{R})\times {10}^{-3}/\mathrm{B}\mathrm{W}$

$(1)$

式中，C表示水产品中的锑含量(ng·g⁻¹)，IR表示水产品的每日摄入量(g·d⁻¹)，BW表示人体平均体重(kg)，以60 kg作为成人平均体重。不同人群的水产品摄入量差异较大，本文综合2020年中国统计年鉴^[22]、中国膳食指南^[23]以及Gulkowska等的研究^[24]，将IR分为一般摄入量（47.7—75.6 g·d⁻¹）、推荐摄入量（75 g·d⁻¹）、高摄入量（235 g·d⁻¹），并将Gulkowska等研究^[24]中不同类型水产摄入量占比(鱼类、贝类和虾的占比分别为44.7%、32.3%、23.0%)应用于上述3种摄入量，以进行更准确的评估。

采用目标危害系数(Target hazard quotient, THQ)评估锑暴露的非致癌风险。如果THQ<1，表明评估项目对居民没有明显的健康风险。如果THQ≥1，则评估项目对人体存在有潜在的健康风险，应采取防护措施。THQ越高意味着经历长期非致癌性危害的可能性越高。THQ计算公式如式(2)。

$\mathrm{T}\mathrm{H}\mathrm{Q}=\sum (C\times \mathrm{I}\mathrm{R})\times \mathrm{E}\mathrm{F}\times \mathrm{E}\mathrm{D}\times {10}^{-3}/(\mathrm{R}\mathrm{f}\mathrm{D}\times \mathrm{B}\mathrm{W}\times \mathrm{T}\mathrm{A})$

$(2)$

式中，EF为暴露频率(365 d·a⁻¹)，ED为总暴露时间(70 a)，RfD为口服参考剂量，TA为非致癌物的平均接触时间(ED×365 d·a⁻¹)。美国环境保护署(USEPA)规定锑的口服参考剂量为0.4 μg·kg⁻¹·d⁻¹^[25]。

1.5 数据统计分析

采用SPSS 18.0软件对实验数据进行统计分析。Kolmogorov–Smirnov检验表明，目标数据不符合正态分布。因此，采用Kruskal–Wallis H检验来评估锑含量在城市或物种间的显著差异性。当锑含量存在显著差异时，使用Mann-Whitney U检验来确定组间的差异。使用Spearman相关性分析探讨锑含量与个体身体特征(长度、重量、水分和脂肪含量)的关系，当P<0.05时，差异具有统计学意义。本文中样品的锑含量均以湿重计。样品中目标物含量低于检出限时，以0代替，便于数据统计分析。

2. 结果与讨论(Results and discussion)

2.1 水产品中的锑含量

采自国内8个典型沿海城市的124份市售水产品样品中锑的检出率为64.5%，其含量范围为<0.13—37.8 ng·g⁻¹（平均值5.70 ng·g⁻¹，中位值2.89 ng·g⁻¹），远低于中国香港食物掺杂(金属杂质含量)规例标准(锑的最高限量值为1000 ng·g⁻¹)^[26]，表明中国沿海城市水产品污染程度低。山东烟台市水产品锑的检测结果同样也表明该沿海城市海产品中未出现锑污染^[15]。现阶段国内外对于水产品中锑污染情况的其他研究主要集中在矿区^{[6-7, 27-30]}，这些地区锑污染严重，例如湖南锡矿山，作为世界上储量最大的锑矿，当地鱼体中锑平均含量则达15 ng·g⁻¹（59.8 ng·g⁻¹干重，以75%含水率换算）^[6]，受采矿污染的南非Olifants河中鱼体内锑的最高含量更是高达28600 ng·g⁻¹ ^[29]，远远高于本次研究鱼体中锑的最高含量（7.40 ng·g⁻¹）。

不同城市市售水产品中锑含量分布如图1a所示，其平均含量由高到低排序为舟山市(12.7 ng·g⁻¹)、宁波市(10.2 ng·g⁻¹)、温州市(6.94 ng·g⁻¹)、深圳市(6.84 ng·g⁻¹)、盐城市(3.59 ng·g⁻¹)、福州市(3.21 ng·g⁻¹)、台州市(2.42 ng·g⁻¹)、杭州市(2.27 ng·g⁻¹)。经Kruskal–Wallis H检验发现各个城市之间水产品中的锑含量并无显著差异(P<0.05)，这与之前关于这些地区水产品中汞和硒的研究结论一致^[31]，这一现象可归因于多种因素，包括：(1)研究中的采样城市主要集中在中国东部；(2)市场所售的水产品多为人工养殖产品，其生长时间较短，对于污染物的累积时间较少；(3)沿海海洋系统中的锑含量被海流均匀化；(4)一些水生生物对锑的积累能力较弱，即使采样地点受到人为污染，生物体中的锑浓度也可能很低^[14]。

图 1 (a)中国八个沿海城市水产品中和(b)三类水产品（鱼、贝类及虾）中的锑含量

Figure 1. Concentrations of Sb (a) in aquatic products from eight coastal cities in China, and (b) in three categories (fish, shellfish and shrimp)

下载: 全尺寸图片幻灯片

不同类别水产品中锑的赋存具有明显差异。锑在贝类和虾中的检出率分别达98.5%和87.5%，而鱼中检出率仅为16.0%。鱼肉中锑的含量(平均0.57 ng·g⁻¹)明显低于贝类(9.40 ng·g⁻¹)和虾(7.30 ng·g⁻¹)(图1b)，这可能与不同生物的锑积累转化能力、生活习性及栖息环境有关。现阶段对此研究较少，有研究指出锑的毒理作用及生物行为与砷相似^{[6, 32]}。贝类对于砷的同化吸收能力要比鱼类强^[33-34]，推测贝类对于锑的同化吸收能力也可能比鱼类强。底栖生物对锑的累积能力比浮游生物强^[18]，贝类大多栖息于水底沉积物中，沉积物通常沉积了大量重金属和类金属，贝类更容易通过接触沉积物富集锑。在贝类中，腹足类的锑含量(平均值13.5 ng·g⁻¹)高于双壳类(8.57 ng·g⁻¹)，可能是由于腹足类通常以藻类及双壳类为食。

为揭示个体对水产品中锑累积的影响，本研究对锑含量与个体身体特征(长度、重量、水分和脂肪含量)进行了Spearman相关性分析。如图2所示，仅在贝类脂含量与锑含量之间存在有明显的负相关性(y=−1.5856x+15.9793, N=66, R²=0.12, P<0.05)，并未发现锑含量和其他身体特征之间存在显著相关性，说明个体身体特征对水产品中锑积累的影响较小。

图 2 水产品样品个体身体特征与锑含量之间的相关性(NS表示无显著相关性)

Figure 2. Relationship between individual body characteristics and concentrations of Sb in the aquatic product samples

下载: 全尺寸图片幻灯片

2.2 鱼体不同部位中的锑含量

由于生物体不同部位对金属的吸收、调节、储存、生物转化和排泄作用不同，锑在鱼体不同器官或组织中的分布具有差异性。如表1所示，在大多数样品中，鱼鳃中锑的检出率和含量较高，其后是肝脏和肌肉，鱼皮和鱼籽中锑均无检出。这一结果与先前的研究结果一致^{[6, 19]}。鱼鳃中的锑含量高于其他器官，这可能与鱼鳃的离子调节作用有关。由于鱼鳃组织表面积大，含有大量的主动运输泵，可从外部水环境运输离子进来，同时鳃组织可以分泌黏液，是捕获金属的结合点。此外，鱼鳃具有排泄作用，会导致更多的锑被转运至鱼鳃中^[19]。关于砷、铜等金属的研究发现，当经由食物暴露途径时，鱼鳃中的金属浓度通常低于其他器官^[35-36]。在本研究中，鱼鳃中的锑浓度较高，而包括肝脏在内的其他器官中的锑含量很低（大多低于检出限），暗示着所研究鱼摄入锑的主要途径并非食物暴露途径，鱼体中锑主要来源于水体中锑。

表 1 中国市售鱼体不同部位中的锑含量

Table 1. Concentrations of Sb in different parts of the marketed aquatic products in China

品种Species	部位Parts	锑含量/(ng·g⁻¹)Sb concentrations	品种Species	部位Parts	锑含量/(ng·g⁻¹)Sb concentrations
罗非鱼	肌肉	ND. ^a	昂刺鱼	肌肉	ND.
	肝脏	2.47		肝脏	ND.
	鱼皮	ND.		鱼皮	ND.
	鱼鳃	14.7		鱼鳃	35.3
珍珠斑	肌肉	ND.	鮰鱼	肌肉	1.60
	肝脏	ND.		肝脏	ND.
	鱼皮	ND.		鱼皮	ND.
	鱼鳃	3.77		鱼鳃	14.3
桂鱼	肌肉	ND.	龙头鱼	肌肉	ND.
	肝脏	1.84		肝脏	2.37
	鱼皮	ND.	鲫鱼	肌肉	ND.
	鱼鳃	25.9		鱼皮	ND.
鳊鱼	肌肉	ND.		鱼籽	ND.
	肝脏	7.32	黄鱼	肌肉	ND.
	鱼皮	ND.		鱼皮	ND.
	鱼籽	ND.		鱼籽	ND.
^a ND (not detected) 表示未检出.

| Show Table

DownLoad: CSV

2.3 食用风险评价

中国8个沿海城市居民锑的平均EDI、 THQ、及鱼类、贝类和虾对THQ的相对贡献占比见图3。3种水产品食用水平下采样城市居民锑的平均EDI分别为0.002—0.014、0.002—0.017、0.006—0.053 μg·kg⁻¹·d⁻¹，远低于由美国环境保护署规定的锑口服参考剂量(0.4 μg·kg⁻¹·d⁻¹)。同时，各个城市居民在3种消费模式下的THQ均小于1。该结果表明，即使是水产品高摄入人群，例如渔民，通过水产品消费所产生的锑暴露风险也可以忽略不计，人体健康不会受到危害。在绝大多数采样城市中，贝类食用是通过水产品摄入锑的THQ主要贡献来源，占比达到39.4%—88.4%，鱼和虾的占比分别在0.4%—13.7%和2.71%—55.2%范围内。因此，在考虑减少通过食用水产品摄入的锑时，可优先减少贝类的食用量。总体而言，对于中国沿海城市居民来说，水产品中锑污染水平处于安全限值以内，可以放心食用，不必担心水产品中的锑暴露风险。

图 3 一般、推荐、高的水产品食用水平下，中国八个沿海城市居民锑的(a)平均每日摄入评估量(EDI)、(b)目标危害系数(THQ)、及(c)鱼类、贝类和虾的THQ贡献比例

Figure 3. (a) Mean estimated daily intake (EDI), (b)target hazard quotient (THQ) of Sb from aquatic product consumption for residents in sampling cities in China under general, recommend and high intake consumption scenarios, and (b) relative contributions of fish, shellfish and shrimp to the THQ

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3. 结论(Conclusion)

本研究分析了中国8个典型沿海城市市售水产品中锑的分布特征及其食用风险。虽然在大多数市售水产品中能够检测到锑，但锑含量普遍较低。与空间区域因素及个体体征相比，物种、生活习性及栖息环境对水产品锑的积累起着更重要的作用。鱼鳃中锑含量较高，说明鱼鳃是鱼类累积锑的主要器官，同时暗示食物暴露并非鱼体摄入锑的主要途径。健康风险评估结果表明，所采样地区居民食用水产品所导致的锑暴露风险可以忽略不计。尽管如此，考虑到锑被广泛应用于各种工业行业，所造成的环境污染越来越严重，仍需要持续关注水产品中锑含量变化以防控相关健康风险。

图 1 水体中全氟化合物的来源

Figure 1. Sources of PFASs in the liquid environment

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图 2 海洋表面微表层-气溶胶的PFASs富集现象

Figure 2. Enrichment of PFASs in ocean surface microsurface-aerosols

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表 1 文献中的新兴多氟及全氟烷基化合物

Table 1. Emerging polyfluorinated and perfluoroalkyl compounds reported in literatures

名称Name	简称Abbreviation	分子式Molecular formula	地点Place	CAS	参考文献Reference
短链全氟烷基磺酸及全氟烷基羧酸Short chain perfluorooctane sulfonates and perfluorooctanoic acids
全氟戊酸Perfluoropentanoic acid	PFBA	C₄F₉COOH	西班牙	2706-90-3	[49]
全氟已酸Perfluorohexanoic acid	PFHxA	C₅F₁₁COOH	中国	307-24-4	[50]
全氟丁烷磺酸Perfluorobutanesulfonic acid	PFBS	C₄F₉SO₃H	中国	375-73-5	[5]
多氟烷基化合物Polyfluoroalkyl compounds
1H,1H,2H,2H-全氟辛磺酸1H,1H,2H,2H-perfluorooctane sulfonic acid	6:2FTS	C₆F₁₃CH₂CH₂SO₃H	中国	27619-97-2	[51]
全氟和多氟烷醚类化合物Perfluoropolyethers
4- 8-二氧-3H-全氟辛酸铵 Ammonium 4,8-dioxa-3H-perfluorononanoate	ADONA	CF₃O（CF₂）₃OCHFCF₂COO^－NH₄ ⁺	中国	958445-44-8	[52]
全氟（2-甲基-3-氧杂己酸）Undecafluoro-2-methyl-3-oxahexanoic acid	HFPO-DA（Gen-X）	C₃F₇OCF（CF₃） COOH（C₃F₇OCF（ CF₃ ） COO^－NH₄⁺）	中国	13252-13-6	[52]
全氟-2,5-二甲基-3,6-二氧杂壬酸Perfluoro（2,5-dimethyl-3,6-dioxanonanoic）acid	HFPO-TA	C₃F₇OC₆F₇OCF（CF₃ ） COOH	中国	13252-14-7	[52]
6:2 氯代多氟烷醚磺酸盐6:2 chlorinated polyfluoroalkyl ether sulfonate	6:2 Cl-PFAES（F-53B）	Cl（CF₂） nO（CF₂）₂SO₃H	中国	756426-58-1	[53]
环状全氟烷基化合物Cyclic perfluorinated acid
十氟-4-（五氟乙基）环氧己烷磺酸钾盐Perfluoroethylcyclohexanesulfonate	PFECHS	C₂F₅C₆F₁₀SO₃^-K⁺	澳大利亚	335-24-0	[54]

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表 2 五大洋中典型PFASs的赋存水平

Table 2. Spatial characteristics of PFASs around the area of the five oceans

大洋Ocean	地区Area	主要PFASsMain PFASs	检出浓度/（pg·L⁻¹）Concentration	参考文献References
大西洋Altantic Ocean	Bay of Biscay of Argentia	PFOAPFOS	PFOA 77—980PFOS 40—250	[67]
大西洋Altantic Ocean	the River Weser	PFOAPFOS	∑PFAAs 120—260	[68]
太平洋Altantic Ocean	the River Qingshui	PFOAPFOS	PFOA 3—420	[69]
太平洋Altantic Ocean	Tokyo Bay	PFOAPFOS	PFOA 48—192PFOS 8—59	[70]
印度洋Indian Ocean	Bay of Bengal coast	PFOAPFOS	∑PFAAs 10.6—46.8	[11]
印度洋Indian Ocean	Between Asia and Antarctica	PFOAPFOS	PFOA 1—441PFOS 5—23.9	[71-72]
北冰洋Arctic Ocean	European High Arctic	PFOAPFDA	∑PFAAs 0.1—3.6	[39]
北冰洋Arctic Ocean	the Central Arctic	PFOAPFOS	∑PFAAs 11—174	[13]
南冰洋Antarctic Ocean	Antarctic Peninsula coast	PFOAPFOS	PFOA 0—25PFOS 25—45	[64]
南冰洋Antarctic Ocean	Coastal Livingston Island	PFHpA PFOA	∑PFAAs 94—420	[73]

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表 3 长江流域PFASs污染状况

Table 3. Contamination status of PFASs in the Yangtze River Basin

	地区Area	检出PFASs总浓度/（ng·L⁻¹）Concentration	主要PFASsMain PFASs	主要PFASs检出浓度/（ng·L⁻¹）Concentration of main PFASs	参考文献Reference
上游	岷江	1.54—30.2	PFBA	0.16—28.4	[74]
	青藏高原峡谷区	0.272—2.224	PFBA	0.272—1.796	[75]
	宜昌段	＜20	PFOA	＜10	[76]
中游	武汉段	4.16—4.77	PFBS	1.28—1.49	[77]
	洞庭湖	18.07—29.95	PFBAPFOA	4.63—11.593.22—8.53	[78]
	洪湖	25.45—63.39	PFOAPFHxAPFBA	6.25—12.392.88—30.674.92—10.95	[78]
	荆州、岳阳、武汉、鄂州、黄石段	2.2—74.56	PFOAPFBS	9.9—161.1—40	[76]
下游	太湖	10.0—119.8	PFOAPFHxA	2.2—74＜0.4—22	[79]
	九江至上海段	3.62—31.91	PFOA	6.8—8.2	[76]
	黄浦江	39.2—576.2	PFOAPFOS	1.0—403＜286	[80]

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表 4 几个典型水体中PFASs年度浓度总和对比

Table 4. Comparison of total PFASs concentrations （ng·L⁻¹） in typical surface water samples

地点Area	取样时间Sampling time	ΣPFASs/（ng·L⁻¹）	统计物质Statistical substance	PFOA/（ng·L⁻¹）	PFOS/（ng·L⁻¹）	参考文献Reference
太湖Lake Taihu	2009—2010	80.3	PFBS、PFHxS、PFOS、PFBA、PFPeA、PFHxA、PFHpA、PFOA、PFNA、PFDA	33.2	13.8	[83]
	2011—2012	67.8		25.3	9.26
	2015	213		71	13.8
	2021	339		120	28.5
巢湖Lake Chao	2002	15.2	PFHpA、PFOA、PFNA、PFDA、PFUnA、PFDoA、PFHxS、PFOS、 PFOSA	5.9	6.6	[150]
	2011	9.56	PFBA、PFPeA、PFHxA、PFHpA、PFOA、PFNA、PFDA、PFUdA、PFBS、PFHxS、PFOS	5.34	0.05	[151]
	2012	21.19		12.68	0.25	[151]
	2019	55.1	PFBA、PFPeA、PFHxA、PFHpA、PFOA、PFNA、PFDA、PFUnDA、PFDoDA、PFTeDA、PFBS、PFHxS、PFOS	12.6	1.15	[152]
安大略湖Lake Ontario	2012	11.86	PFBA、PFPeA、PFHxA、PFHpA、PFOA、PFNA、PFDA、PFUnA、PFDoA、PFBS、PFHxS、PFOS	2.37	3.95	[153]
	2013	13.21		2.52	5.07
	2015	15.58		2.23	5.15
易北湖Lake Eble	2011	8.1	PFBS、PFHxS、PFOS、PFBA、PFPeA、PFHxA、PFOA、PFNA、PFDA	1.9	0.91	[154]
	2013—2014	16.8	PFBS、PFHxS、PFOS、PFBA、PFPeA、PFHxA、PFHpA、PFOA、PFNA、PFDA、PFUnDA、PFDoDA、6：2FTS、FOSA、HFPO-TA	1.9	ND	[69]
	2015	26.82	PFBA、PFPeA、PFBS、PFHxA、PFHpA、PFHxS、PFOA、PFHpS、PFNA、PFOS、PFDA、PFUnDA、PFDS、PFDoDA、PFTrDA、PFTeDA	2.37	ND	[155]
注：ND，未检出，not detected.

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[156]	LI L, ZHAI Z H, LIU J G, et al. Estimating industrial and domestic environmental releases of perfluorooctanoic acid and its salts in China from 2004 to 2012 [J]. Chemosphere, 2015, 129: 100-109. doi: 10.1016/j.chemosphere.2014.11.049
[157]	CHEN H R, PENG H, YANG M, et al. Detection, occurrence, and fate of fluorotelomer alcohols in municipal wastewater treatment plants [J]. Environmental Science & Technology, 2017, 51(16): 8953-8961.
[158]	YAO J Z, SHENG N, GUO Y, et al. Nontargeted identification and temporal trends of per- and polyfluoroalkyl substances in a fluorochemical industrial zone and adjacent Taihu Lake [J]. Environmental Science & Technology, 2022, 56(12): 7986-7996.
[159]	SHI B, WANG T Y, YANG H F, et al. Perfluoroalkyl acids in rapidly developing coastal areas of China and South Korea: Spatiotemporal variation and source apportionment [J]. Science of The Total Environment, 2021, 761: 143297. doi: 10.1016/j.scitotenv.2020.143297
[160]	DU D, LU Y L, ZHOU Y Q, et al. Perfluoroalkyl acids (PFAAs) in water along the entire coastal line of China: Spatial distribution, mass loadings, and worldwide comparisons [J]. Environment International, 2022, 169: 107506. doi: 10.1016/j.envint.2022.107506
[161]	MENG L Y, SONG B Y, ZHONG H F, et al. Legacy and emerging per- and polyfluoroalkyl substances (PFAS) in the Bohai Sea and its inflow rivers [J]. Environment International, 2021, 156: 106735. doi: 10.1016/j.envint.2021.106735
[162]	SHAN G Q, QIAN X, CHEN X, et al. Legacy and emerging per- and poly-fluoroalkyl substances in surface seawater from northwestern Pacific to Southern Ocean: Evidences of current and historical release [J]. Journal of Hazardous Materials, 2021, 411: 125049. doi: 10.1016/j.jhazmat.2021.125049
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[165]	ZHAO Z, TANG J H, XIE Z Y, et al. Perfluoroalkyl acids (PFAAs) in riverine and coastal sediments of Laizhou Bay, North China [J]. Science of the Total Environment, 2013, 447: 415-423. doi: 10.1016/j.scitotenv.2012.12.095

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1. 材料与方法（Materials and methods）
1.1 样品采集和预处理
1.2 分析方法
1.3 质量保证与质量控制
1.4 健康风险评价
1.5 数据统计分析
2. 结果与讨论(Results and discussion)
2.1 水产品中的锑含量
2.2 鱼体不同部位中的锑含量
2.3 食用风险评价
3. 结论(Conclusion)

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全氟及多氟烷基化合物（per- and polyfluoroalkyl substances，PFASs）是一类人工合成的有机氟化物，其结构上至少存在一个完全氟化的甲基（—CF₃）或亚甲基（—CF₂—）碳^[1]. 由于C-F键极高的化学键能（460 kJ·mol⁻¹）^[2]，PFASs具有极强的稳定性，同时具有疏水疏脂、耐高温、耐氧化的性质，能在自然环境中长久稳定地存在^[3].

据统计，人工合成的PFASs已逾4700种，仅2000年至2017年，就有超过3000 t PFASs被合成，并被用于塑料、橡胶、电子工业产品以及油漆的生产^[4]. 长期的生产使用使得PFASs不断在环境中积累，目前，在中国东南部地区河流水^[5]、约旦Zarqa河两岸土壤^[6]、北极圈大气^[7]等全球范围环境介质中内均有PFASs检出. 研究表明，环境中的PFASs可以通过饮用水和食物链传递作用进入人体，并造成生殖系统损伤^[8]、免疫系统损伤^[9]以及神经性伤害^[10]. 全氟辛烷磺酸（perfluorooctane sulfonate，PFOS）和全氟辛酸（perfluorooctanoic acid，PFOA）是环境中最典型的两种PFASs，分别于2009年和2019年被正式列入《斯德哥尔摩公约》. 与此同时，欧盟2015年颁布的《水框架指令》中规定地表水中PFOS年平均浓度不得超过0.65 ng·L⁻¹，最大浓度不得超过65 ng·L⁻¹；2016年，美国环境保护署（EPA）设立了饮用水中PFOS和PFOA总浓度低于70 ng·L⁻¹的健康标准. 2014年我国原环保部和农业部等12部委发布的文件要求，五年内确保PFOS在特定豁免用途全部淘汰. 在《重点管控新污染物清单（2021年版）》中重申，禁止PFOS类物质生产，并严禁生产、使用和进出口PFOA类物质. 尽管PFOS、PFOA等长链PFASs已被限制生产使用，仍有大量短链或含有其他新兴PFASs替代品被不断开发应用，环境中可检出PFASs种类不断增加，如何解决PFASs污染已逐渐成为当下最受关注的环境问题之一.

环境水体是环境中PFASs的重要储存库^[11-12]，由于PFASs分子结构的特殊性，PFASs在水环境中的分布及其与不同环境介质的结合状态相比传统疏水有机污染物差异较大^[13-15]. 此外，水的地球循环过程、水力作用也会影响PFASs的环境迁移与转化过程^[16-17]. 因此，厘清PFASs在水环境中的迁移转化规律，并揭示多种环境介质对该过程的影响，对于科学评估PFASs的环境污染现状并进一步有效治理PFASs污染具有重要科学意义. 在过去的数十年间，有关PFASs的综述研究已有较多，例如，Gagliano、Wei、 Bolan等^[18-25] 总结比较了PFASs在大气、土壤及水环境中的修复技术，包括吸附法、水热法、超声法、光降解及生物降解法等. Podder 等^[26-28]对现有研究中PFASs的潜在暴露途径及生物毒性进行了总结. 此外，Kurwadkar等^[29-32]回顾了PFASs在自然水环境中的污染浓度和分布特征、暴露及现场分析方法. 上述研究总结归纳了已有研究中报道的PFASs检测分析手段、修复技术，或是针对特定区域、环境介质、单一类别PFASs进行了统计分析，而对于全球尺度上地表水中全类别PFASs的污染水平研究依然缺乏. 本文总结归纳了多种地表水体中PFASs污染现状与时空分布特征，概述了地表水体中PFASs的主要来源及迁移规律，并揭示了影响该过程的多个环境要素及作用机制，为后续研究PFASs在环境中的迁移转化过程提供理论支撑，并对未来新型PFASs研发方向与监测手段进行了展望.

1. 地表水中PFASs的污染现状（Pollution status of PFASs in surface water）

2. 地表水中PFASs污染空间分布特征及归趋成因分析（The temporal distribution in surface water bodies and the analysis of the causes）

3. 地表水中PFASs污染时间分布特征及归趋成因分析（The spatial distribution in surface water bodies and the analysis of the causes）

3.1. 地表水中PFASs赋存水平的季节性变化

水中PFAS浓度的季节性变化受到许多因素的影响，例如水流量，水质特性，气温以及集水区PFAS的使用和排放. Yu等观测到太湖水体中的PFASs，在雨季时的总浓度高达157 ng·L⁻¹，超过旱季（72 ng·L⁻¹）的两倍^[83]. 研究人员认为，降雨多时，云滴内的PFASs可通过湿沉降进入地表水，同时冲刷附着在大气颗粒物上的PFASs，使得大气中的PFASs沉降下来，进入地表水或者土壤中，造成大气中PFASs的清除和地表水中PFASs的升高^[145]，同时，在雨水充沛的夏季，降雨和由此产生的地表径流将陆地上的PFASs汇入湖中，进一步加剧水体污染^[80]. 此其，典型的雨季高温可以加速PFAAs前体的降解转化，在强烈的太阳辐射驱动下，太湖中高浓度PFASs前体物质生化转换加快，导致雨季太湖PFASs的总浓度上升^[146]. 降水量增多的雨季，土壤中污染物随着雨水下渗的风险提高，径流量增大，水动力加快，底泥中的污染物冲进水体，从而使得PFASs的检出浓度高于旱季^[147]. 水利工程等人类活动也是造成水体PFASs季节性特征的一大重要因素：“长江至太湖引水工程”流经常熟市的氟化工厂分布密集的望屿河，夏季引水将向太湖拱湖湾输入过量的PFASs^[83].

在沿海地区，由于台风衍生的连续密集降雨（因此含有较少的陆地颗粒）和纳潮量的提升共同加速了雨季的海水交换能力，沿海水体中PFASs与内陆水体往往呈现相反的季节性变化^[148]. Cai等发现了福建九龙口处的∑PFASs浓度呈现：旱季>雨季，雨季沿海地区PFASs浓度最低^[149]，胶州湾沿海海水中的PFAS浓度也在旱季呈现最高水平^[148].

3.2. 地表水中PFASs赋存水平的年度变化

表4总结了近年来部分典型内陆水体中PFASs浓度年度变化趋势^{[69, 83, 150-155]}. 显然， PFCAs与PFSAs是水体中PFASs污染的主体，大部分水体中PFASs总量呈现逐年波动上升的趋势. 近年来，由于氟化工相关行业向中国转移并飞速发展^[156]，湖泊中的PFASs流入量急剧增加，加之湖泊水力停留时间长，从而延迟PFASs生产和使用变化的响应时间，导致这类污染物在被淘汰后，浓度依然不断上升. PFCAs被证实还可通过前体物质或者其他结构的PFASs转化而来^[157]，这是水体中PFCAs的又一潜在来源，也是PFASs总量逐年攀升的原因之一.

不同地区湖泊中， PFOA与PFOS在浓度变化趋势有些许不同. 对于PFOA：在中国，PFOA污染逐年加重，Yu等测得太湖流域2015年的全氟烷基羧酸与磺酸总量骤升至213 ng·L⁻¹， PFOA单体浓度在这期间同样增加^[83]. Yao等比较发现，太湖中PFOA浓度由2016年的18.0 ng·L⁻¹增长至2021年的28.2 ng·L^{−1 [158]}. PFOA的逐年增长现象同样在加拿大的安大略湖、德国易北湖中被观察到，但增长速率更慢. 而对于PFOS，在中国湖泊中，PFOS增长率较PFOA更缓慢，而北美、欧洲国家，湖泊中的PFOS污染开始逐渐减轻，总量开始下降. 这可能得益于北美等地区对PFOS、PFOA和其他长链全氟烷基羧酸盐（PFCAs）及其前体物质的较早地采取了管控措施.

为满足持续的工业需求，大量新兴PFASs投入使用，新兴PFASs污染逐渐加重. 如在中国和韩国快速发展的沿海地区，河流中长链PFASs逐渐被短链PFASs取代，在韩国，短链C4—C7 的PFCAs 的比例由2008—2012年的46%增长到2018年的79%，主要的全氟烷基磺酸由传统PFOS转变为新兴短链型PFBS^[159-160]. 多氟烷基磺酸FTSs、Cl-PFESAs等都曾作为PFOS的替代品，被投入使用后进入环境中被大量检出^{[52, 161]}. 值得注意的是，相关政策出台带来的产业化调整，会引导企业研发更替新兴PFASs，导致在这一时期的调查中某一特定PFASs浓度的异常升高^[17].

近年来，海洋水体中PFASs污染仍在加重^[161-162]. 洋流源源不断地将陆源PFASs输送至全球海洋水体，加之近年的气候变化加速了PFASs迁移转化速度. PFASs污染逐年加重这一现象在极地水体中尤为明显. 极地海冰中的PFASs可能随着融冰过程重新释放到海水中，成为极地水体的PFASs新来源^[40]. 同时，因气温上升，大洋绕极环流、极锋带等对极地地区的生物隔离被破坏，促使更多PFASs以生物迁移方式向极地传输，从而导致极地海洋水体PFASs浓度上升. 例如，迁徙鸟类在南极以外区域暴露和富集PFASs，回迁后通过产蛋、生物残渣、粪便使其体内的PFASs残留在南极地区^[163].

4. 总结与展望（Conclusion and prospect）

近年来，多项限制PFASs生产与使用的措施被采纳，但传统PFASs的残余库存、转化和浸出，都有可能使得水环境中的PFASs浓度在停用几年后继续升高，这种传统PFASs污染防治的滞后性与新兴多氟及全氟替代物的不断更新生产，给未来的PFASs污染治理提出了更高要求. 目前大范围、长时间维度的监测数据的匮乏与检测手段、监测技术的不足，厘清PFASs在地表水中的赋存特征及时空差异性，对完善监测体系、深入理解PFASs的全球传输机制及后续治理PFASs具有重要意义.

本文通过概述全氟及多氟烷基化合物（PFASs）在地表水中的赋存现状，为健全PFASs监测管理体系与后续PFASs治理方案提供新思路. 本文综述了内陆河道、湖泊及海洋中的PFASs环境赋存水平，强调了点源污染对地表水PFASs污染的重要性，建议建立完善的PFASs的源头防治措施；概要分析了水体PFASs时空赋存差异性的成因以及影响因素，为提高监测数据稳定性、排除数据偶然性，宏观准确把握各水体污染现状提供了参考；同时指出：新兴 PFASs在地表水体中已普遍存在，并且已经显现出一定的替代趋势，部分研究表明这类物质的毒性已无法忽略^[164].

（1）新兴PFASs替代品及其代谢产物的检测技术亟需完善整合：现有研究多基于测定具有标准试剂的物质，开发合成新兴PFASs标准品或获得该物质的公开信息，将成为这部分物质及其降解、衍生产物的成功定性分析和定量检测的关键.

（2）深入研究新兴PFASs替代品在环境中的转化产物及探明其转化路径，或有机会实现新兴PFASs替代品生物降解，相应地也可为研发新的无潜在生物蓄积性、无毒性、易降解的高性能化合物提供新方向.

（3）对PFASs在沿海/海洋沉积物中的监测调查亟待加强：沉积物是水体中PFASs的次要来源，目前在河道中水-沉积物上的分配机制研究较多，而对海洋中的研究较少. 海洋具有独有的地貌特征、洋流驱动，海洋/沿海沉积物中PFASs的沉积系数与河流沉积物具有较大差异^[165]，使得各预测模型对PFASs浓度预测值与实际值相差甚远. 故亟需强化监测技术并在这些地区开展持续性监测.

参考文献 (165)

地表水中全氟及多氟烷基化合物（PFASs）的污染现状研究进展

通讯作者: E-mail：zhchen@nju.edu.cn

Research progress on the pollution status of per-and polyfluoroalkyl substances (PFASs) in surface water: A review

Corresponding author: CHEN Zhanghao, zhchen@nju.edu.cn

1. 材料与方法（Materials and methods）

1.1 样品采集和预处理

1.2 分析方法

1.3 质量保证与质量控制

1.4 健康风险评价

1.5 数据统计分析

2. 结果与讨论(Results and discussion)

2.1 水产品中的锑含量

2.2 鱼体不同部位中的锑含量

2.3 食用风险评价

3. 结论(Conclusion)

计量

出版历程

地表水中全氟及多氟烷基化合物（PFASs）的污染现状研究进展

通讯作者: E-mail：zhchen@nju.edu.cn

English Abstract

Research progress on the pollution status of per-and polyfluoroalkyl substances (PFASs) in surface water: A review

Corresponding author: CHEN Zhanghao, zhchen@nju.edu.cn

全文HTML

1.1. 内陆河流湖泊中PFASs的污染现状

1.2. 海洋中PFASs的污染现状

2.1. 内陆江河湖泊中的PFASs污染地域分布特征及归趋成因分析

2.2. 海洋中的 PFASs污染地域分布特征及归趋成因分析

2.3. 地表水中的垂直分布特征及归趋成因分析

2.3.1. 江河湖泊中的PFASs垂直分布特征及归趋成因分析

2.3.2. 海洋中的PFASs垂直分布特征及成因分析

3.1. 地表水中PFASs赋存水平的季节性变化

3.2. 地表水中PFASs赋存水平的年度变化

目录

全文HTML

1.1. 内陆河流湖泊中PFASs的污染现状

1.2. 海洋中PFASs的污染现状

2.1. 内陆江河湖泊中的PFASs污染地域分布特征及归趋成因分析

2.2. 海洋中的 PFASs污染地域分布特征及归趋成因分析

2.3. 地表水中的垂直分布特征及归趋成因分析

2.3.1. 江河湖泊中的PFASs垂直分布特征及归趋成因分析

2.3.2. 海洋中的PFASs垂直分布特征及成因分析

3.1. 地表水中PFASs赋存水平的季节性变化

3.2. 地表水中PFASs赋存水平的年度变化