稳定同位素在污染物溯源与示踪中的应用

由于稳定同位素在特定污染源中组成确定,且具有分析结果精确可靠、在污染物迁移与转化过程中不发生显著变化的特点,故已被广泛应用于环境污染事件的仲裁、环境污染物的来源分析与示踪研究中。介绍了稳定同位素分馏对于来源分析的影响以及稳定同位素技术在污染物溯源与示踪中识别大气多环芳烃来源、推测环境中硫和铅的来源、考察甲基叔丁基醚来源与降解过程等方面的应用进展。     

传统稳定同位素技术在环境科学领域的应用及研究进展

本文回顾了同位素技术的发展历史、简介了传统稳定同位素技术的应用原理与主要分析仪器.重点介绍了传统稳定同位素技术在污染物溯源、识别转化历程和指示反应程度,以及重建古环境信息,构建生态系统营养结构和探索生态物质循环等环境科学领域的应用与最新研究进展,提出了当前传统稳定同位素技术面临的挑战并对未来的发展方向进行了展望.     

脑部外源性颗粒态污染物的识别与追踪

大量流行病学研究表明大气细颗粒物污染的长期暴露与脑血管、行为障碍、神经退行性疾病等脑部疾病的发生或恶化关系密切,然而,目前关于脑部外源性颗粒态污染物的认识仍近乎“黑箱”状态,这已成为准确认识环境污染对脑部健康风险研究的瓶颈问题.本文综述了当前脑部外源性污染物,特别是颗粒态污染物研究的最新进展,提出基于非靶向分析技术、同位素追踪技术等建立脑部外源性颗粒态污染物识别、表征和溯源的系统研究方法,解析入脑外源性颗粒态污染物信息,追踪典型污染物入脑的暴露途径、跨生物屏障转运、代谢归趋及生命周期.为进一步阐明外源性颗粒态污染物对脑部重要生理功能及生命过程的扰动机制提供方法学支撑和科学支持.     

鱼体中有机微污染物的定量及筛查研究进展

化学品通过多种途径进入环境水体,可对水生生物及人体健康造成潜在风险。鱼类作为水环境污染物监测的指示生物,分析鱼体内有机微污染物的分布特征是评估水环境安全的重要方法。现有污染物种类繁多,且在生物体内存在降解转化的过程,基于靶向定量分析的监测方法难以系统、准确地评估鱼体中有机污染物的暴露特征。由于具有高分辨率、高质量精度、高通量和回顾性分析等特点,高分辨质谱技术逐渐被用于鱼体中有机污染物的筛查研究,为鱼体中高风险及未知污染物的定性、定量分析提供可能。本文综述了鱼体中有机污染物的定量分析现状,筛查分析方法以及其在鱼体中有机微污染物筛查研究中的应用。     

水体被动采样技术的发展与应用

被动采样技术不需要任何外力,具有操作简单、安全可靠等特点,在环境领域表现出良好的应用前景.本文回顾了水体被动采样技术的发展历程,简要介绍了被动采样技术定量方法,介绍并讨论了典型无机、有机水体被动采样装置特点、应用和发展趋势.其中,沉积物-水界面有机污染物被动采样以及水体无机/有机污染物被动采样是近些年被动采样技术的重要发展方向.最后,对水体被动采样技术在构型设计、应用范围、理论推进、与生物分析结合以及方法标准化方面的发展前景进行了展望.     

巢湖生态系统中微量有机污染物的研究进展

本文综述了目前巢湖生态系统中微量有机污染物研究的主要进展。巢湖微量有机污染物研究起步较晚,但发展较快。目前已研究的微量有机污染物包括有机氯农药、多氯联苯、多环芳烃、多溴联苯醚、邻苯二甲酸酯、全氟烷基酸类物质、四溴双酚A、抗生素和有机磷农药。研究内容主要包括水、大气、降尘、沉积物、悬浮物、水生生物等多介质分布、来源解析、跨界面迁移、归趋模拟与风险评估等方面。期望本文的综述,可以为巢湖微量有机污染物风险管理和水质改善提供重要决策支撑,对于在其他湖泊开展此类研究有所裨益。     

多溴联苯醚(PBDEs)光降解研究现状

多溴联苯醚(polybrominated diphenyl ethers,PBDEs)为一类新型的持久性有机污染物,因其在环境中的广泛分布和生物累积性而备受关注,环境中PBDEs的降解也成为研究热点.光降解是自然环境中PBDEs降解的主要途径之一,而光降解过程中会形成毒性更高的溴代二英.本文在总结国内外PBDEs光降解研究的基础上,对影响PBDEs光降解的因素(诸如:分子结构、光源、介质等)、途径和产物,特别是溴代二英的形成进行了综述,对目前存在问题及进一步的研究方向进行了讨论和展望.     

环境中多溴联苯醚分析方法的研究进展

多溴联苯醚(PBDEs)是一类性能优异的阻燃剂,被广泛添加到工业产品和日常生活用品中.研究表明很多PBDEs单体具有持久性有机污染物(POPs)的特性,其中五溴和八溴联苯醚已被列入POPs清单.它们在环境中广泛存在,对环境和生态系统带来健康风险.本文概述了环境中PBDEs的前处理方法和仪器分析的研究进展,对不同的方法进行了综述和比较,并提出了PBDEs分析方法研究的发展趋势.     

脂环族溴代阻燃剂的生物富集、代谢及毒性效应研究进展

以六溴环十二烷（HBCD）为代表的脂环族溴代阻燃剂（CBFRs）被广泛应用于纺织、建材、电子、电气、化工、交通、建材等领域.随着HBCD作为《关于持久性有机污染物的斯德哥尔摩公约》增列持久性有机污染物,与HBCD具有相似结构和性能的四溴环己烷（TBECH）和四溴环辛烷（TBCO）等CBFRs被当作HBCD的潜在替代产品.迄今为止,HBCD、TBECH和TBCO已在大气、水体、土壤等多种环境介质和生物体中被检出,它们在生物体内的代谢转化以及内分泌干扰、神经、生殖、发育等毒性效应亦受到广泛关注.值得指出的是,所有CBFRs均含有同分异构体,表现出异构体选择性的生物富集、代谢和毒性效应.遗憾的是,目前相关研究还十分匮乏.本文从CBFRs的环境暴露水平、生物富集、毒性效应、以及CBFRs的生物转化等方面展开综述,特别强调了从异构体水平研究HBCD及其替代物的必要性.本文有助于全面了解CBFRs生物富集、代谢及毒性效应,对于正确认识和准确评价CBFRs的生态和健康风险具有重要的科学意义.     

土壤中持久性有机污染物不可提取态残留的测试方法、生成特征与环境风险研究进展

持久性有机污染物（persistent organic pollutants,POPs）是一类具持久性、高生物蓄积性、高毒性且具长距离迁移性的高关注度化学物质，土壤是其主要储存库. POPs进入土壤后，与土壤结合发生老化现象，一部分生成不可提取态残留（non-extractable residue,NER）.作为POPs环境归趋中的重要过程，NER的生成传统上被视为污染物的去毒或降解途径；但随着老化时间的增加或者受环境条件变化等因素的影响，土壤中NER可能会再次释放，造成环境风险.国内外有关土壤有机污染物NER的研究已有较多报道，但其中关于POPs-NER的报道相对欠缺.本文介绍了POPs-NER的同位素测试手段和生成机理，对特定组分NER的测试方法、POPs-NER生成的动力学模型与影响因素以及POPs-NER的释放与环境风险等方面的研究进展进行了综述，并简要分析了当前POPs-NER研究领域的局限和未来需要关注的问题.由于部分研究方向缺乏POPs-NER的案例，本文分析了一些非持久性有机污染物NER的相关研究，以期为今后POPs-NER的研究提供参考.     

Whole pictures of halogenated disinfection byproducts in tap water from China’s cities

When bromide/iodide is present in source water, hypobromous acid/hypoiodous acid will be formed with addition of chlorine, chloramine, or other disinfectants. Hypobromous acid/hypoiodous acid undergoes reactions with natural organic matter in source water to form numerous brominated/iodinated disinfection byproducts (DBPs). In this study, tap water samples were collected from eight cities in China. With the aid of electrospray ionization-triple quadrupole mass spectrometry by setting precursor ion scans of m/z 35, m/z 81, and m/z 126.9, whole pictures of polar chlorinated, brominated, and iodinated DBPs in the tap water samples were revealed for the first time. Numerous polar halogenated DBPs were detected, including haloacetic acids, newly identified halogenated phenols, and many new/unknown halogenated compounds. Total organic chlorine, total organic bromine, and total organic iodine were also measured to indicate the total levels of all chlorinated, brominated, and iodinated DBPs in the tap water samples. The total organic chlorine concentrations ranged from 26.8 to 194.0 μg·L^–1 as Cl, with an average of 109.2 μg·L^–1 as Cl; the total organic bromine concentrations ranged from below detection limit to 113.3 μg·L^–1 as Br, with an average of 34.7 μg·L^–1 as Br; the total organic iodine concentrations ranged from below detection limit to 16.4 μg·L^–1 as I, with an average of 9.1 μg·L^–1 as I; the total organic halogen concentrations ranged from 31.3 to 220.4 μg·L^–1 as Cl, with an average of 127.2 μg·L^–1 as Cl.     

环境空气中短链氯化石蜡研究进展

短链氯化石蜡(SCCPs)是碳链长度为10至13个碳原子的正构烷烃氯代衍生物。SCCPs具有持久性、生物累积性、长距离迁移能力、以及毒性作用。SCCPs已被《关于持久性有机污染物的斯德哥尔摩公约》增列为持久性有机污染物审查范围内,引起了全球关注。SCCPs在环境各介质及生物体内均有检出,近年来,在室内空气和灰尘中也检出了大量SCCPs,其已成为人体暴露的一个重要来源。本文就大气环境及室内空气与灰尘中氯化石蜡(CPs)的采样与分析方法、污染水平与来源,及人体暴露概况进行了综合阐释,以期为我国大气和室内环境中CPs的研究工作提供参考。     

The emergence of stable isotopes in environmental and forensic geochemistry studies: a review

In the past decade, environmental forensics has emerged as a discipline directed toward determining parties liable for causing spills of contaminants into the environment. Such investigations, while geared toward determining the guilty parties in order to recover costs of the cleanup and remediation, require various questions to be addressed. These include determination of the nature of the product; Where did it come from?; Extent of weathering, if any; How long has it been there?; and Is it degrading naturally? Traditionally, these studies have been addressed through utilization of techniques such as gas chromatography (GC) and gas chromatography–mass spectrometry (GCMS). However, in recent years, stable isotopes, primarily determined through the use of combined gas chromatography–isotope ratio mass spectrometry (GCIRMS), have emerged as an equally important tool in environmental forensics. For relatively low molecular, volatile compounds such as MTBE, BTEX, or chlorinated solvents, the isotopes, primarily carbon and hydrogen, have been used extensively for evaluating the onset of natural attenuation. For larger molecules such as PCBs or PAHs, in which the effects of biodegradation on the isotope composition of these molecules is minimal, the isotopic fingerprints of the individual compounds can be used for correlation purposes. In this paper, a brief introduction to isotope geochemistry will be given, followed by a review of applications of stable isotopes to a variety of environmental problems. While the review may not necessarily be exhaustive, it will provide a comprehensive overview of areas where isotopes have been used and potential applications for the future. Most of the review is concerned with carbon and hydrogen isotopes, although a brief overview of the emerging area of chlorine isotopes will also be discussed.     

Sources of halogens in the environment,influences on human and animal health

Of the halogens, fluorine has the highest crustal abundance (544 mg/kg) while iodine has the lowest (0.25 mg/kg), however, chlorine is by far the most abundant halogen in the cosmos. The geochemistries of the four naturally occurring halogens have some similarities with fluorine, chlorine and bromine being classified as lithophile elements while iodine is more chalcophile in nature. Bromine and iodine behave in a similar fashion in the secondary environment and could be classified as biophile elements being concentrated in organic matter. Chlorine, bromine and iodine are strongly enriched in the sea while iodine and to a lesser extent bromine are further concentrated in the marine algae.Apart from the occurrence of fluorine in fluorite (CaF₂) there are few commonly occurring minerals which contain the halogens as essential constituents. In the igneous environment fluorine and chlorine tend to occupy hydroxyl lattice sites in micas, amphiboles, apatites etc., while in sediments clays can contain appreciable quantities of these elements. Bromine and iodine, however, would be unlikely to fit into the lattice sites of common rock-forming minerals.Bromine, like iodine, is probably volatilised from the marine environment and is carried on to land surfaces. This behaviour of iodine and bromine is reflected in the increased I/CI and Br/CI ratios of surface run-off in continental compared with near coastal environments.Limited information on the soil geochemistry of the halogens suggests that the soil contents of chlorine, bromine and iodine are influenced by proximity to the sea. Soil fluorine, however, is generally dependent on its content in the parent material. In some areas pollutant sources of the halogens contribute appreciably to their concentration in the environment.Iodine and chlorine are essential elements for mammals and fluorine has been shown to have beneficial effects on bone and tooth formation. However, excess quantities of dietary fluorine can be harmful. It is possible, in view of its ubiquitous occurrence in the biosphere, that bromine has a hitherto unknown function in human and animal health.     

Die rolle der umweltprobenbank in der Umweltüberwachung am beispiel von chlorierten kohlenwasserstoffen in ausgewählten matrizes

For precautinary environmental protection the Environmental Specimen Bank (ESB) has been successfully established as a permanent environmental surveillance tool in Germany. The presented monitoring results on chlorinated hydrocarbons (CHC) show very clearly the effects of political decisions and can be used for the identification of pollutant sources. The CHC burden of breams (Abramis brama) from five German rivers (Elbe, Rhein, Saar, Mulde, Saale) gives an current overview of the pollution situation of different limnic ecosystems in Germany. A calculation model about the distribution of organic pollutants between different tissues offers the possibility to predict concentrations in liver and muscle of breams. Legislative emission restrictions have led to a significant decrease of dioxin levels in herring gull (Larus argentatus) eggs between 1988–1996.     

珠三角地区POPs农药的污染现状及控制对策

概述了中国及国际社会对持久性有机污染物（Persistent Organic Pollutants,POPs）的关注情况。并通过对POPs农药在珠江三角洲地区（Pearl River Delta Area,PRD）使用情况的调查，以及对珠江三角洲地区POPs农药在各环境介质中的污染现状的文献综述，结合环境污染数据以及POPs农药污染调查工作中得到的数据和信息，对该地区POPs污染的可能原因和环境中可能存在的新近污染源进行了初步探讨。同时也指出了当前珠江三角洲地区在POPs农药削减与淘汰工作中所遭遇到的缺乏完善的管理体系等困难，并针对问题提出了包括加大科研投入，加强基础研究，掌握污染物来源和去向，加强替代药物的研究，建立和实施更严格的环境法规以及标准，加强环境监测能力建设，建立POPs农药污染的信息公开机制等一系列的控制对策。     

环境中短链和中链氯化石蜡的来源、污染特征及环境行为研究进展

短链氯化石蜡(SCCPs)是持久性有机污染物,已于2017年5月被正式列入《关于持久性有机污染物的斯德哥尔摩公约》附件A的受控名单.中链氯化石蜡(MCCPs)具有相似的性质.由于氯化石蜡(CPs)大量生产以及广泛应用,其在环境介质中的含量处于较高水平.本文综述了SCCPs和MCCPs的生产和排放,以及2016年以后文献报道的SCCPs和MCCPs在不同环境介质中的研究进展,包括在大气、水体、土壤和沉积物中的赋存、分布特征,探讨了SCCPs和MCCPs的环境行为,同时指出环境中CPs的溯源、界面过程及区域传输是未来的主要研究方向.     

Catalytic decomposition of polychlorinated biphenyls (PCBs)

In this study, polychlorinated biphenyls (PCBs) were decomposed by low‐temperature heat treatment with metallic catalyst, and with metallic catalyst and a hydrogen source. Of the catalysts used, iron (Fe) was the most active catalyst for the decomposition of PCBs, and the decomposition was due to dechlorination. The addition of hydrogen sources accelerated the decomposition of PCBs in the presence of catalyst. Surface analysis of the catalyst using X‐ray photoelectron spectroscopy (XPS) suggested that the emitted chlorine was presumed to form metal chloride. The reactions of each homolog can be expressed by a successive first‐order reaction model. This means that a substituted chlorine is successively detached during this reaction. The overall decomposition rate in this reaction system was controlled by that of the lower chlorinated homologs. The decomposition rates with Fe and NaBH₄ for the lower chlorinated homologs were about 10 times as fast as the rates with only Fe.     

Remediation of soil and groundwater contaminated with organic chemicals using stabilized nanoparticles: Lessons from the past two decades

▪ Overviewed evolution and environmental applications of stabilized nanoparticles. ▪ Reviewed theories on particle stabilization for enhanced reactivity/deliverability. ▪ Examined various in situ remediation technologies based on stabilized nanoparticles. ▪ Summarized knowledge on transport of stabilized nanoparticles in porous media. ▪ Identified key knowledge gaps and future research needs on stabilized nanoparticles. Due to improved soil deliverability and high reactivity, stabilized nanoparticles have been studied for nearly two decades for in situ remediation of soil and groundwater contaminated with organic pollutants. While large amounts of bench- and field-scale experimental data have demonstrated the potential of the innovative technology, extensive research results have also unveiled various merits and constraints associated different soil characteristics, types of nanoparticles and particle stabilization techniques. Overall, this work aims to critically overview the fundamental principles on particle stabilization, and the evolution and some recent developments of stabilized nanoparticles for degradation of organic contaminants in soil and groundwater. The specific objectives are to: 1) overview fundamental mechanisms in nanoparticle stabilization; 2) summarize key applications of stabilized nanoparticles for in situ remediation of soil and groundwater contaminated by legacy and emerging organic chemicals; 3) update the latest knowledge on the transport and fate of stabilized nanoparticles; 4) examine the merits and constraints of stabilized nanoparticles in environmental remediation applications; and 5) identify the knowledge gaps and future research needs pertaining to stabilized nanoparticles for remediation of contaminated soil and groundwater. Per instructions of this invited special issue, this review is focused on contributions from our group (one of the pioneers in the subject field), which, however, is supplemented by important relevant works by others. The knowledge gained is expected to further advance the science and technology in the environmental applications of stabilized nanoparticles.