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全氟和多氟化合物及溴代芳香化合物的生物累积研究
Alternative TitleBioaccumulation of perfluoroalkyl and polyfluoroalkyl substances (PFASs) and brominated aromatic compounds
刘艳伟
Subtype博士
Thesis Advisor江桂斌 ; 刘稷燕
2019-06
Degree Grantor中国科学院生态环境研究中心
Place of Conferral北京
Degree Name理学博士
Degree Discipline环境科学
Keyword全氟和多氟化合物,多溴二苯醚,溴酚,生物累积,食物链行为 pfass, Pbdes, Bromophenols, Bioaccumulation, Trophic Transfer
Abstract

       人工合成的重要表面活性剂全氟和多氟化合物( Perfluoroalkyl and polyfluoroalkyl substances,PFASs)和溴代阻燃剂多溴二苯醚(Polybrominated diphenyl ethers,PBDEs)被广泛应用在人们的生产和生活中,其中一些单体因具有环境持久性、长距离迁移能力、生物累积和毒害作用被列为持久性有机污染物(Persistent organic pollutants,POPs)。尽管这些化合物的生产和使用受到限制,但其带来的环境问题将长期存在,对生态系统和人类健康产生深远的影响。同时,这些环境污染物的一些转化产物,例如PBDEs 的转化产物OH-/MeO-PBDEs 和溴酚(Bromophenols,BrPs),具有与母体化合物相似的化学结构和毒理效应。此外,一些新型替代物也存在环境持久性和生物累积能力,例如PFOS(Perfluorooctanesulfonic acid)的潜在替代物氯代多氟醚基磺酸盐(Chlorinated polyfluoroalkyl ether sulfonates,Cl-PFAESs)。目前关于这些转化产物和新型替代物的环境赋存、行为和风险的研究非常匮乏。
      本论文工作围绕PFASs 和PBDEs 这两类持久性有机化合物,以及其多种转化产物和新型替代物展开,探究了这些化合物在陆生植物和海洋食物链中的赋存现状、生物累积特性和食物链行为,评估了这些化合物的生态风险和膳食暴露风险,对于阐明复杂来源卤代有机污染物的环境来源、行为和风险有重要意义。

      植物吸收和累积大气卤代有机污染物对于污染物的环境迁移、转化和归趋非常重要。第一部分研究工作针对不同种类树皮样品中PFASs 的累积行为展开,发现全氟羧酸化合物(Perfluorocarboxylic acids,PFCAs)和全氟磺酸化合物(Perfluoroalkyl sulfonic acids,PFSAs)在树皮样品中广泛存在,而Cl-PFAESs和全氟-4-乙基环己烷磺酸盐(Perfluoro-4-ethylcyclohexane sulfonate,PFECHS)等新型污染物仅在个别样品中检出。PFASs 在树皮中呈现显著的物种差异性累积,其中油松树皮累积更多的短链PFCAs 和PFSAs,加杨、垂柳和国槐树皮对长链单体的累积更显著。进一步研究表明不同种类树皮的化学组成和表面形貌差异会造成气相和颗粒相PFASs 的截留差异,从而导致不同植物样品吸收、去除和累积大气污染物的差异。第二部分研究工作探究了溴酚在北京植物样品中的赋存现状和累积特征。溴酚在北京植物叶片和树皮中广泛检出。大叶冬青和小叶黄杨叶片中检测到3-monoBrP、4-monoBrP、2,4-diBrP 和3,5-diBrP,树皮样品中检测到4-monoBrP、2,4-diBrP、2,4,6-triBrP 和3,4,5-triBrP。溴酚的单体组成表明植物样品中溴酚的来源非常复杂,包括天然源和人为源。此外,间位取代的3-monoBrP、3,5-diBrP 和3,4,5-triBrP 揭示了植物中的溴酚部分来自PBDEs 等化合物的环境转化。
       渤海生态系统受到众多河流和沿海地区排放的污染物的影响,本论文探究了多种卤代有机化合物在渤海海洋生物中的赋存现状、累积特征和食物链行为,并评估了这些化合物的海产品膳食暴露风险。针对PFASs 的研究发现渤海生物中新型污染物Cl-PFAESs 的浓度水平虽然显著低于常见PFCAs 和PFSAs,但其在各种生物体内均有检出,在软体动物中呈现逐年上升趋势。6:2 Cl-PFAES 的生物累积和分布特征与常见PFASs 相似,呈现显著的生物放大效应,意味着该类新型污染物具有潜在的生态和健康风险。对溴代阻燃剂PBDEs 和其转化产物OH-/MeO-PBDEs 累积行为的研究表明一些生物体内OH-/MeO-PBDEs 的浓度水平与PBDEs 相当甚至更高。OH-PBDEs 呈现显著的生物稀释效应,而MeO-PBDEs与PBDEs 在高营养级鱼类体内发生显著的生物累积。这些现象与化合物的环境来源和化学性质有关,表明海洋生物中OH-/MeO-PBDEs 主要来自藻类和低等无脊椎动物合成等天然来源。膳食暴露风险评估研究发现天然产生的OH-/MeO-PBDEs 的膳食摄入量与人为源的PBDEs 相当。由于OH-PBDEs 具有更高的生物毒性,并且可以从MeO-PBDEs 和PBDEs 转化而来,因而这些天然化合物的高摄入可能导致更高的健康风险。

Other Abstract

      Perfluoroalkyl and polyfluoroalkyl substances (PFASs) and polybrominated diphenyl ethers (PBDEs) have been widely applied in industrial and commercial products. These compounds have attracted wide attention due to their environmental persistence, long distance transport, bioaccumulation and toxicity. Despite the ongoing regulation, the ecological risks and adverse health effects caused by these pollutants will last for a long period. Meanwhile, some metabolites of these persistent pollutants are also toxic and accumulative, such as bromophenols (BrPs), OH-PBDEs and MeO-PBDEs. In addition, emerging halogenated compounds are produced to replace those persistent and toxic compounds. For example, as a potential alternative for perfluorooctanesulfonic acid (PFOS), chlorinated polyfluoroalkyl ether sulfonates (Cl-PFAESs) were found very persistent and bioaccumulative. However, there are limited studies focusing on the occurrences, bioaccumulation potentials and environmental risks of these metabolites and alternatives.
       The environmental occurrences, bioaccumulation potentials, trophic transfer behaviors and potential risks of various halogenated organic pollutants were investigated in terrestrial plants and marine food chains. The target compounds included PFASs, PBDEs and some of their metabolites and alternatives. This research work was of great significance to elucidate the environmental behaviors and ecological risks of various halogenated organic pollutants.
      As plant absorption and accumulation of atmospheric organic pollutants are important for pollutants’ environmental fates, this research work firstly focused on bioaccumulation of PFASs in plant samples collected from Beijing. It was found that perfluorocarboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs) were ubiquitous in tree bark, whereas emerging pollutants, Cl-PFAESs and perfluoro-4-ethylcyclohexane sulfonate (PFECHS), were rarely detected. Species-dependent tree bark accumulation patterns were observed for PFCAs and PFSAs. Short-chain congeners were more accumulated in pine bark, whereas long-chain congeners were at higher levels in bark samples from Canadian poplar, weeping willow and Chinese scholartree. Further studies identified that the discrepancies of chemical compositions and surficial structures of different tree bark samples led to the retention discrepancies of gaseous and particle-bound PFASs,resulting in different contribution to the absorption, removal and migration of atmospheric pollutants.
      Bromophenols, a class of emerging pollutants, were also investigated in plant samples collected from Beijing. 3-monoBrP, 4-monoBrP, 2,4-diBrP and 3,5-diBrP were detected in leaves of Buxus microphylla and Ilex latifolia, whereas 4-monoBrP, 2,4-diBrP, 2,4,6-triBrP and 3,4,5-triBrP were detected in bark samples from all the four sampled tree species. Bromophenols were detected in nearly all leaf and bark samples, suggesting the wide occurrence of bromophenols in the surrounding environment. The sources for bromophenols may be very complex, including the natural source and anthropogenic source. And the detection of meta-substituted 3-monoBrP, 3,5-diBrP and 3,4,5-triBrP suggested bromophenols were partly transformed from PBDEs and other brominated organic compounds.

      The marine ecosystem from Chinese Bohai Sea was intensively affected by pollutants released from over 40 rivers and coastal areas, thus the occurrences, accumulation potentials and trophic transfer behaviors of various halogenated compounds were investigated in marine organisms collected from Bohai Sea. The emerging pollutant, Cl-PFAESs have been used as the mist suppressant in China for 40 years. It was found that the concentration of Cl-PFAESs in Bohai Sea organisms was significantly lower than that of commonly concerned PFSAs and PFCAs. Despite the low contamination level, Cl-PFAESs were widely detected in marine organisms collected from Bohai Sea, and also showed an increasing trend these years. Besides,Cl-PFAESs showed similar accumulation patterns in various marine organisms to the commonly concerned PFASs. Furthermore, a significant biomagnification potential was observed for 6:2 Cl-PFAES, indicating the potential ecological risk of this emerging pollutant.
       The brominated flame retardant PBDEs and their transformation products,OH-PBDEs and MeO-PBDEs, were also investigated in marine biota from Bohai Sea,China. OH-PBDEs and MeO-PBDEs showed similar or even higher concentrations to PBDEs in marine organisms. OH-PBDEs showed significant trophic dilution, while MeO-PBDEs and PBDEs were both at higher concentrations in high trophic fish.These results were tightly related to the environmental sources and physicochemical properties of different compounds, which also indicated OH-/MeO-PBDEs in marine organisms mainly originated from natural sources. The dietary exposure assessment of OH-/MeO-PBDEs through seafood consumption demonstrated that the average daily intake of natural OH-/MeO-PBDEs was comparable to that of anthropogenic PBDEs. Since OH-PBDEs have higher toxicity and can be transformed from MeO-PBDEs and PBDEs, dietary intakes of these natural chemicals may lead to severer health risks.

Pages152
Language中文
Document Type学位论文
Identifierhttp://ir.rcees.ac.cn/handle/311016/42257
Collection环境化学与生态毒理学国家重点实验室
Recommended Citation
GB/T 7714
刘艳伟. 全氟和多氟化合物及溴代芳香化合物的生物累积研究[D]. 北京. 中国科学院生态环境研究中心,2019.
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