生态环境学报 ›› 2023, Vol. 32 ›› Issue (12): 2115-2127.DOI: 10.16258/j.cnki.1674-5906.2023.12.004
郝丽宇1(
), 何苗苗2, 汤家喜1,3,*()
收稿日期:2023-08-16
出版日期:2023-12-18
发布日期:2024-02-05
通讯作者:
*汤家喜。E-mail: tangjiaxi1986@163.com作者简介:郝丽宇（1997年生），女，硕士研究生，研究方向为环境污染与生态修复。E-mail: hly12345ssdlh@163.com
基金资助:
HAO Liyu1(), HE Miaomiao2, TANG Jiaxi1,3,*()
Received:2023-08-16
Online:2023-12-18
Published:2024-02-05
摘要：
全氟化合物（PFASs）是一类具有特殊结构的新型环境污染物，作为一种人工合成的持久性有机化合物，已被广泛应用于消防、工业等多领域，因其对环境的持久性和生物毒性而受到全球关注。PFASs在自然环境中不易降解，且具有一定的亲水性，导致河流水体成为了PFASs的重要的源和汇，对水环境造成了一定的危害。近年来，国内外学者研究并提出了多种有效去除PFASs的修复技术，以减轻其对环境和人体的有害影响。该文简述了PFASs的来源，氟化工企业是环境介质中PFASs的重要来源之一。分析了PFASs在河流水体中的污染现状，河流水体中PFASs的主要来源为点源和非点源，然而非点源污染，尤其是胶体载带PFASs的污染也应加以关注并亟待解决。阐明了河流水体中PFASs的来源与迁移途径，其中工业园区是PFASs的主要来源。该文还总结了水环境中PFASs的物理化学修复技术（吸附技术、过滤技术、化学氧化技术、光化学氧化技术，电化学氧化技术和声化学技术），并对比分析了不同修复技术作用效果的优缺点及未来的发展方向。重点探究了水环境中PFASs非点源的原位修复技术（河岸过滤系统、植物修复技术、人工湿地和生态缓冲带）的修复效果及作用机制。在此基础上，提出了生物炭与生态缓冲带联合修复技术，阻控水环境中PFASs非点源污染，并对其技术的潜力进行了展望。该文旨在为河流水体中PFASs的修复技术提供有效的支持和建议。
中图分类号:
郝丽宇, 何苗苗, 汤家喜. 河流水体全氟化合物的污染现状及修复技术研究进展[J]. 生态环境学报, 2023, 32(12): 2115-2127.
HAO Liyu, HE Miaomiao, TANG Jiaxi. Research Progress on Pollution Situation and Remediation Technology of Perfluoroalkyl Substances in River Water[J]. Ecology and Environment, 2023, 32(12): 2115-2127.
| 名称 | 基本结构 |
|---|---|
| PFOA 全氟辛酸 | |
| PFOS 全氟辛烷磺酸 | |
| PFNA 全氟壬二酸 | |
| PFDA 全氟癸酸 | |
| PFUnDA 全氟十一酸 | |
| PFDoDA 全氟十二烷酸 | |
| PFTrDA 全氟十三酸 | |
| PFTDA 全氟十四酸 | |
表1 常见的PFASs
Table 1 Common PFASs
| 名称 | 基本结构 |
|---|---|
| PFOA 全氟辛酸 | |
| PFOS 全氟辛烷磺酸 | |
| PFNA 全氟壬二酸 | |
| PFDA 全氟癸酸 | |
| PFUnDA 全氟十一酸 | |
| PFDoDA 全氟十二烷酸 | |
| PFTrDA 全氟十三酸 | |
| PFTDA 全氟十四酸 | |
图1 PFASs主要迁移过程
Figure 1 Major migration processes of PFASs
| 流域 | PFASs数量 | 质量浓度/(ng∙L−1) | 参考文献 | ||
|---|---|---|---|---|---|
| ∑PFASs | PFOS | PFOA | |||
| 印度南部流域 | 13 | 0.39‒3.32 | 0.19‒0.65 | 0.23‒1.06 | Selvaraj et al., |
| 洛东江 (韩国) | 12 | 0.22‒73.90 | 0.12‒33.20 | 0.12‒42.20 | Lam et al., |
| 易北河 (德国) | 17 | 7.10‒27.60 | 0.50‒2.90 | 2.80‒9.60 | Ahrens et al., |
| 布里斯班河 (澳大利亚) | 7 | 0.83‒40.00 | 0.18‒15.00 | 0.13‒1.60 | Gallen et al., |
| 红河 (越南) | 10 | 4.00‒17.00 | 0.18‒5.30 | 0.09‒18.00 | Duong et al., |
| 长江 (中国) | 18 | 2.20‒174.56 | 0.23‒12.22 | 6.81‒15.61 | Pan et al., |
| 黄河 (中国) | 17 | 7.75‒121.63 | 0.95‒15.37 | 0.96‒14.15 | Wang et al., |
| 珠江 (中国) | 13 | 3.00‒52.00 | 0.71‒8.70 | 0.56‒11.00 | Zhang et al., |
| 松花江 (中国) | 15 | 6.40‒32.00 | ND | ND‒1.70 | Zhang et al., |
| 海河 (中国) | 9 | 12.00‒174.00 | 2.02‒17.62 | 14.40‒42.10 | Li et al., |
| 大凌河 (中国) | 11 | 1.77‒9540.00 | 0.16‒483.00 | ND‒2280.00 | Zhu et al., |
| 辽河 (中国) | 11 | 44.40‒781.00 | 0.09‒9.50 | 0.67‒61.60 | Chen et al., |
表2 国内外流域水体中溶解态PFASs的质量浓度水平
Table 2 Concentration levels of dissolved PFASs in waters of domestic and international watersheds
| 流域 | PFASs数量 | 质量浓度/(ng∙L−1) | 参考文献 | ||
|---|---|---|---|---|---|
| ∑PFASs | PFOS | PFOA | |||
| 印度南部流域 | 13 | 0.39‒3.32 | 0.19‒0.65 | 0.23‒1.06 | Selvaraj et al., |
| 洛东江 (韩国) | 12 | 0.22‒73.90 | 0.12‒33.20 | 0.12‒42.20 | Lam et al., |
| 易北河 (德国) | 17 | 7.10‒27.60 | 0.50‒2.90 | 2.80‒9.60 | Ahrens et al., |
| 布里斯班河 (澳大利亚) | 7 | 0.83‒40.00 | 0.18‒15.00 | 0.13‒1.60 | Gallen et al., |
| 红河 (越南) | 10 | 4.00‒17.00 | 0.18‒5.30 | 0.09‒18.00 | Duong et al., |
| 长江 (中国) | 18 | 2.20‒174.56 | 0.23‒12.22 | 6.81‒15.61 | Pan et al., |
| 黄河 (中国) | 17 | 7.75‒121.63 | 0.95‒15.37 | 0.96‒14.15 | Wang et al., |
| 珠江 (中国) | 13 | 3.00‒52.00 | 0.71‒8.70 | 0.56‒11.00 | Zhang et al., |
| 松花江 (中国) | 15 | 6.40‒32.00 | ND | ND‒1.70 | Zhang et al., |
| 海河 (中国) | 9 | 12.00‒174.00 | 2.02‒17.62 | 14.40‒42.10 | Li et al., |
| 大凌河 (中国) | 11 | 1.77‒9540.00 | 0.16‒483.00 | ND‒2280.00 | Zhu et al., |
| 辽河 (中国) | 11 | 44.40‒781.00 | 0.09‒9.50 | 0.67‒61.60 | Chen et al., |
图2 PFASs进入人体途径
Figure 2 Route of entry of PFASs into the human body
| 修复技术 | 材料 | 过程 | 优缺点 | 参考文献 |
|---|---|---|---|---|
| 吸附 | 吸附材料 (活性炭、改性生物质、树脂等) | 选用不同种类的吸附剂来吸附PFASs, 以达到去除的效果 | 去除效果好, 但操作维护成本高 | Nzerib et al., |
| 过滤 | 过滤材料 (纳滤膜和反渗透膜等) | 常用反渗透膜和纳滤膜分离PFASs | 去除效果好, 操作简单, 但膜的替换与高质量浓度滞留液的处理会使成本增高 | Rahman et al., |
| 高级氧化技术AOPs | 氧化剂(过氧化氢、过硫酸钠、高锰酸钾、高锰酸钠、臭氧等) | 使溶液中产生强氧化性的羟基-OH, 与溶液中的PFASs反应, 转化成为无毒可降解的副产物 | 反应速度慢, 成本高, 氧化过程中产生的短链PFASs可能造成二次污染, 可与其他方法结合使用 | Park et al., |
| 光化学氧化技术 | 紫外线，可见光等 | 利用紫外线或可见光产生水合电子来去除PFASs | 绿色环保, 可减少二次污染, 但效率低, 成本高, 无法大规模使用 | Chen et al., |
| 电化学氧化技术 | 电极 (石墨烯, 二氧化铅、氧化钛、二氧化锡等) | 通过直接或间接阳极氧化, 将PFASs吸附在电极上, 被电极直接降解, 或与其他液体反应进行降解 | 去除效率高, 反应时间短, 但反应过程中会产生短链PFASs和有毒副产物, 成本高 | Wang et al., |
| 声化学技术 | 超声辐射 | 高级氧化处理的一种, 利用超声波辐照形成高温气泡与氧化性强的物质来降解PFASs | 无法大规模使用, 成本高，受外界影响因素多 (如溶液pH、黏滞系数、表面张力系数、溶液温度等) | Dorrance et al., |
表3 水环境中PFASs的物理化学修复技术
Table 3 Physicochemical remediation of PFASs in the aquatic environment
| 修复技术 | 材料 | 过程 | 优缺点 | 参考文献 |
|---|---|---|---|---|
| 吸附 | 吸附材料 (活性炭、改性生物质、树脂等) | 选用不同种类的吸附剂来吸附PFASs, 以达到去除的效果 | 去除效果好, 但操作维护成本高 | Nzerib et al., |
| 过滤 | 过滤材料 (纳滤膜和反渗透膜等) | 常用反渗透膜和纳滤膜分离PFASs | 去除效果好, 操作简单, 但膜的替换与高质量浓度滞留液的处理会使成本增高 | Rahman et al., |
| 高级氧化技术AOPs | 氧化剂(过氧化氢、过硫酸钠、高锰酸钾、高锰酸钠、臭氧等) | 使溶液中产生强氧化性的羟基-OH, 与溶液中的PFASs反应, 转化成为无毒可降解的副产物 | 反应速度慢, 成本高, 氧化过程中产生的短链PFASs可能造成二次污染, 可与其他方法结合使用 | Park et al., |
| 光化学氧化技术 | 紫外线，可见光等 | 利用紫外线或可见光产生水合电子来去除PFASs | 绿色环保, 可减少二次污染, 但效率低, 成本高, 无法大规模使用 | Chen et al., |
| 电化学氧化技术 | 电极 (石墨烯, 二氧化铅、氧化钛、二氧化锡等) | 通过直接或间接阳极氧化, 将PFASs吸附在电极上, 被电极直接降解, 或与其他液体反应进行降解 | 去除效率高, 反应时间短, 但反应过程中会产生短链PFASs和有毒副产物, 成本高 | Wang et al., |
| 声化学技术 | 超声辐射 | 高级氧化处理的一种, 利用超声波辐照形成高温气泡与氧化性强的物质来降解PFASs | 无法大规模使用, 成本高，受外界影响因素多 (如溶液pH、黏滞系数、表面张力系数、溶液温度等) | Dorrance et al., |
图3 河岸过滤系统示意图
Figure 3 Schematic of riparian filtration system
图4 植物修复方法
Figure 4 Phytoremediation methods
图5 人工湿地示意图
Figure 5 Schematic diagram of artificial wetland
图6 生态缓冲带示意图
Figure 6 Schematic diagram of ecological buffer zone
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