持久性有机污染物的分析检测研究进展

持久性有机污染物(POPs)可以通过各种环境介质(大气、水、生物体等)长距离迁移并长期存在于环境中,具有生物富集性、毒性、致畸、致癌性,对人类健康和环境具有严重的危害.用于此类物质的分析方法很多,主要可分为仪器联用分析方法和快速分析方法,如:色谱-质谱分析、光谱分析、生物分析、光/电分析、传感分析等.这些方法各有优缺点,互为补充.本文将按照分析方法,重点介绍2000年至今在POPs分析技术上的最新进展.     

QSAR/QSPR在POPs归趋与风险评价中的应用*

持久性有机污染物(POPs)是目前备受国际社会关注的高危害性有机污染物,对它们的环境归趋分析和风险评价需要获得大量可靠的性质数据和毒性数据,而定量结构活性/性质相关(QSAR/QSPR)方法为快速有效地获得这些数据提供了可能性。QSAR/QSPR模型已在预测POPs的生物活性/性质,补充缺失的基础数据及探求POPs的环境过程机制和生态效应机理等方面得到了广泛应用,近年来也在新POPs物质的筛选、归趋模拟以及风险评价等方面有着更进一步的应用或潜在应用前景。本文介绍了QSAR/QSPR在POPs性质和生物活性预测中的基本应用及其在POPs归趋和风险评价中的扩展应用,并对QSAR/QSPR在POPs研究领域的应用前景进行了展望。     

手性持久性有机污染物的环境界面过程及生态安全研究进展

随着越来越多分子中含有手性结构的持久性有机污染物(POPs)进入环境介质,对其环境界面过程及生态安全的研究已成为环境科学领域的一个热点.目前,有关手性POPs的研究主要集中在外消旋体水平上,在对映体层面研究环境中手性POPs的历史并不长.但由于手性POPs不同对映体在生物学效应方面存在显著的差异,因此,手性POPs环境行为及其潜在生态风险对映体选择性效应更应值得重视.本文将在对映体水平上对手性POPs在各环境介质中的迁移、转化、生物体内的富集以及毒理学效应等方面的研究进行综述.     

持久性有机污染物(POPs)生殖毒理研究进展——从实验动物生殖毒性到人类生殖健康风险

与常规污染物不同,持久性有机污染物(Persistent Organic Pollutants,POPs)在环境中滞留时间长,极难降解,毒性强,可在食物链中富集放大,能通过各种环境介质进行全球性迁移,对人类健康带来巨大危害.POPs对健康的影响是多方面的、复杂的,不仅具有"三致"效应(致癌、致畸、致突变性),而且有内分泌干扰作用,对生殖系统、免疫系统、神经系统等产生毒性.生殖健康不仅关乎人类繁衍,更能对人口素质乃至社会的发展产生深远影响,因此,POPs的生殖毒性以及对人类生殖健康的影响一直备受关注.本文在回顾我国POPs环境污染与人类暴露的研究基础上,结合近年来国内外的研究情况,着重讨论几类典型POPs的生殖毒性和致毒机制以及对人类生殖健康的影响,并对存在的问题和今后的关注点进行总结.     

全二维气相色谱分析持久性有机污染物的应用进展

持久性有机污染物（POPs）组分复杂,在自然界中超痕量存在,其分离分析十分困难。全二维气相色谱（GC×GC）作为一种新型色谱技术,与传统的一维气相色谱相比,具有峰容量大、分辨率和灵敏度高等优势,越来越广泛地应用于环境有机污染物的分析。该文综述了近十年来全二维气相色谱在持久性有机污染物分析中的应用进展,主要包括全二维气相色谱在解决一些复杂POPs定性定量分析难题方面的应用,如二恶英、毒杀芬和短链氯化石蜡等;概述了全二维气相色谱对多种POPs同时定性定量分析的应用进展;讨论了全二维气相色谱在非目标有机污染物筛查分析中的应用,并对发展趋势及相关应用前景进行了总结展望。     

大气持久性有机污染物(POPs)被动采样

大气是进行全球和区域持久性有机污染物(persistent organic pollutants,POPs)观测的良好介质.对<斯德哥尔摩公约>履约效力评估的需求,加速了大气POPs采样技术的研发与应用.大气POPs被动采样技术(passive atmospheric sampling,PAS)在近年来得到了飞速发展,日益成为大流量大气采样的重要补充手段,并显示出其在广大区域范围内实现大气POPs同步观测的优势.本文综述了大气PAS技术的基本原理,介绍、评价了几种主要大气PAS装置,重点分析了PUF-PAS的应用技术原理,介绍了大气PAS在全球各区域和不同研究领域的应用研究进展,分析了大气PAS研究领域的动态,提出了今后大气PAS研究中值得关注的研究内容和趋向.     

短链氯化石蜡的分析方法、污染现状与毒性效应

作为一种新型有机污染物,短链氯化石蜡(SCCPs)在2006年被列入斯德哥尔摩公约持久性有机污染物(POPs)候选名单。2017年5月第8次《关于持久性有机污染物的斯德哥尔摩公约》缔约方大会上,SCCPs最终被列入了《公约》附件A受控POPs清单。我国是氯化石蜡(CPs)生产使用大国,其在环境介质中的含量处于较高水平。本文对SCCPs的分析方法、污染现状、环境中来源与释放及其毒性效应进行了综述,并针对目前存在的问题及研究需求进行了总结。     

气候变化对持久性有机污染物环境过程与生态效应的影响

气候变化对持久性有机污染物(POPs)的影响是目前环境科学领域普遍关注的热点问题。本文介绍了气候变化如何影响POPs向环境的排放、长程传输、环境归趋和对人类与环境的暴露。同时,也强调减缓气候变化的政策和措施与POPs的消除和管理之间的协同作用。为了更好地在国家、区域以及全球成功履行《斯德哥尔摩公约》,本文基于现有的关于POPs和气候变化相互影响效应的知识,从管理和政策层面上给出了建言。     

表面增强拉曼光谱检测二噁英类化合物研究进展

以二噁英及二噁英类多氯联苯为代表的持久性有机污染物(POPs), 具有致畸、致癌、致突变的性质, 被国际癌症研究中心列为人类一级致癌物. POPs通过环境进入食物链对食品安全造成威胁和影响. 以表面增强拉曼光谱(SERS)为代表的新型快速检测技术具有高灵敏分析的特点. 本综述总结了近年来基于SERS技术分析POPs的研究进展, 归纳了不同类型增强基底, 提出了SERS分析POPs的若干关键技术难点, 并对未来SERS技术在POPs分析方面的发展进行了展望.     

水相中POPs光化学降解研究进展

综述了近年来12种持久性有机污染物(POPs)在水体中光化学降解行为,从水体中POPs的光解途径、光解机理和定量结构-性质关系(QSPR)三个方面探讨了POPs在水体中的光化学行为,展望了水体中POPs光化学行为的研究前景.     

Certification of methylmercury content in two fresh-frozen reference materials: SRM 1947 Lake Michigan fish tissue and SRM 1974b organics in mussel tissue (Mytilus edulis)

This paper describes the development of two independent analytical methods for the extraction and quantification of methylmercury from marine biota. The procedures involve microwave extraction, followed by derivatization and either headspace solid-phase microextraction (SPME) with a polydimethylsiloxane (PDMS)-coated silica fiber or back-extraction into iso-octane. The identification and quantification of the extracted compounds is carried out by capillary gas chromatography/mass spectrometric (GC/MS) and inductively coupled plasma mass spectrometric (GC/ICP-MS) detection. Both methods were validated for the determination of methylmercury (MeHg) concentrations in a variety of biological standard reference materials (SRMs) including fresh-frozen tissue homogenates of SRM 1946 Lake Superior fish tissue and SRM 1974a organics in mussel tissue (Mytilus edulis) and then applied to the certification effort of SRM 1947 Lake Michigan fish tissue and SRM 1974b organics in mussel tissue (Mytilus edulis). While past certifications of methylmercury in tissue SRMs have been based on two independent methods from the National Institute of Standards and Technology (NIST) and participating laboratories, the methods described within provide improved protocols and will allow future certification efforts to be based on at least two independent analytical methods within NIST.     

固相萃取-气相色谱-串联质谱法同时测定武汉市普通人群血清中35种有机氯农药与多氯联苯

有机氯农药(OCPs)和多氯联苯(PCBs)是两类重要的持久性有机污染物,可在环境介质中长期存在,并通过多种途径进入人体,导致人体的高暴露风险。OCPs和PCBs对人体存在诸多健康危害,精准定量人体内OCPs和PCBs的暴露水平是健康效应评价的关键。该研究基于固相萃取-气相色谱-串联质谱联用技术(SPE-GC-MS/MS)建立了同时检测100 μL血清中35种OCPs和PCBs的分析方法。血清样品经尿素沉淀蛋白后,采用Oasis^® HLB小柱净化,正己烷-二氯甲烷混合溶液(1∶1, v/v)洗脱,氮吹近干,正己烷定容,多反应监测(MRM)模式检测,内标法定量分析。结果表明,OCPs和PCBs在0.05~50.0 ng/mL范围内线性关系良好,检出限在1.2~71.4 ng/L之间。35种目标分析物的加标回收率在72.6%~142%之间,相对标准偏差小于25%。利用所建立的方法检测了武汉市普通人群血清样本中OCPs和PCBs的浓度水平,结果表明武汉市普通人群广泛暴露于OCPs和PCBs,且以OCPs为主。有8种OCPs和7种PCBs检出率高于50%,其中p,p'-滴滴伊、p,p'-滴滴滴和甲氧滴滴涕检出率达100%,非类二噁英PCBs是PCBs的主要成分。血清中OCPs浓度随年龄增长呈升高趋势,在60岁以上存在性别差异;不同性别、年龄人群血清中PCBs浓度无统计学差异。该方法样本用量少,操作简便,具有较高的准确度和精密度,适用于环境健康研究中大量人群血清样本中痕量OCPs和PCBs的生物监测。     

Separation and preconcentration of persistent organic pollutants by cloud point extraction

Persistent organic pollutants (POPs) are recognized as a class of poisonous compounds which pose risks of causing adverse effects to human health and the environment. Thus, it is very important to detect POPs in environmental and biological samples. The identification and determination of very low levels of POPs in complex matrices is extremely difficult. Recently a promising environmentally benign extraction and preconcentration methodology based on cloud point extraction (CPE) has emerged as an efficient sample pretreatment technique for the determination of trace/ultra-trace POPs in complex matrices. The purpose of this paper is to review the past and latest use of CPE for preconcentrating POPs and its coupling to different contemporary instrumental methods of analysis. First, the comparison of various extraction techniques for POPs is described. Next, the general concept, influence factors and other methods associated with CPE technique are outlined and described. Last, the hyphenations of CPE to various instrumental methods for their determination are summarized and discussed.     

A review of the determination of persistent organic pollutants for environmental forensics investigations

The field of environmental forensics emerged in the 1980s as a consequence of legislative frameworks enacted to enable parties, either states or individuals, to seek compensation with regard to contamination or injury due to damage to the environment. This legal environment requires stringent record keeping and defendable data therefore analysis can sometimes be confined to data to be obtained from certified laboratories using a standard accredited analytical method. Many of these methods were developed to target specific compounds for risk assessment purposes and not for environmental forensics applications such as source identification or age dating which often require larger data sets. The determination of persistent organic pollutants (POPs) for environmental forensic applications requires methods that are selective but also cover a wide range of target analytes which can be identified and quantified without bias. POPs are used in a wide variety of applications such as flame retardants, fire suppressants, heat transfer agents, surfactants and pesticides mainly because of their chemical inertness and stability. They also include compounds such as dioxins that can be unintentionally produced from industrial activities. POPs are persistent in the environment, bioaccumulative and/or toxic and therefore require analytical methods that are sensitive enough to meet the low detection limits needed for the protection of the environment and human health. A variety of techniques, procedures and instruments can be used which are well suited for different scenarios. Optimised methods are important to ensure that analytes are quantitatively extracted, matrix coextractables and interferences are removed and instruments are used most effectively and efficiently. This can require deviation from standard methods which can open the data up to further scrutiny in the courtroom. However, when argued effectively and strict QA/QC procedures are followed the development and optimization of methods based on investigation specific scenarios has the potential to generate better quality and more useful data.     

Chromatographic determination of the rate and extent of absorption of air pollutants by sea water

Summary A simple chromatographic method is developed to determine the rate constant for expulsion of an air pollutant from water or its diffusion parameter in the liquid, the rate constant for chemical reaction of the pollutant with water, its mass transfer coefficient in the liquid, and the partition coefficient between liquid water and air. From these physicochemical parameters, the absorption rate by sea water and, therefore, the depletion rate of a polluting substance from the air can be calculated, together with the equilibrium state of this absorption. The method has been applied to nitrogen dioxide being absorbed by triple-distilled water and by sea water, at various temperatures. From the temperature variation of the reaction rate constant and of the partition coefficient, the activation energy for the reaction and the differential heat of solution were determined.     

多氯联苯的正辛醇-空气分配系数与气相色谱保留参数的关联

通过对19种多氯联苯（PCBs）在DB-1,DB-5和DB-1701等3种色谱柱上的气相色谱（GC）保留参数A,B值与正辛醇-空气分配系数(Koa)的相关分析,发现GC保留参数A,B与Koa存在明显的线性关系。采用了逐步回归的方法,建立了保留参数A,B与Koa的二元回归方程,相关系数的平方达到了0.99以上,标准偏差小于0.11。此外,根据实验测定的153个PCBs的GC保留参数以及定量构效关系（QSAR）研究中的56个预测值,对剩余190种PCBs的Koa值进行了预测。     

Quantitative determination of alpha-tocopherol distribution in a tributyrin/Brij 30/water model food emulsion

Until recently, determining the distribution of antioxidants, AOs, between the oil, interfacial and aqueous regions of opaque emulsions has not worked well because the concentrations of AOs in interfacial regions cannot be determined separately from their concentrations in the oil and water phases. However, our novel kinetic method based on the reaction between an arenediazonium ion and vitamin E, or alpha-tocopherol, provides the first good estimates for the two partition constants that describe alpha-tocopherol distribution between the oil/interfacial and water/interfacial regions of tributyrin/Brij 30/water emulsions without physical isolation of any phase. The reaction is monitored by a new derivatization method based on trapping unreacted arenediazonium ion as an azo dye and confirmed by linear sweep voltammetry, LSV. The results by both derivatization and LSV methods are in good agreement and show that alpha-tocopherol distributes strongly in favor of the interfacial region when the oil is tributyrin, e.g., ca. 90% when the surfactant volume fraction is Phi I=0.01. The second-order rate constant for reaction in the interfacial region is also obtained from the results. Our kinetic method provides a robust approach for determining antioxidant distributions in emulsions and should help develop a quantitative interpretation of antioxidant efficiency in emulsions.     

Analytical chemistry of the persistent organic pollutants identified in the Stockholm Convention: A review

Persistent organic pollutants (POPs) are major environmental concern due to their persistence, long-range transportability, bio-accumulation and potentially adverse effects on living organisms. Analytical chemistry plays an essential role in the measurement of POPs and provides important information on their distribution and environmental transformations. Much effort has been devoted during the last two decades to the development of faster, safer, more reliable and more sensitive analytical techniques for these pollutants. Since the Stockholm Convention (SC) on POPs was adopted 12 years ago, analytical methods have been extensively developed. This review article introduces recent analytical techniques and applications for the determination of POPs in environmental and biota samples, and summarizes the extraction, separation and instrumental analyses of the halogenated POPs. Also, this review covers important aspects for the analyses of SC POPs (e.g. lipid determination and quality assurance/quality control (QA/QC)), and finally discusses future trends for improving the POPs analyses and for potential new POPs.     

Atmospheric pressure chemical ionization in gas chromatography-mass spectrometry for the analysis of persistent organic pollutants

Atmospheric pressure chemical ionization (APCI) was primarily applied as the ion source for liquid chromatography-mass spectrometry (LC–MS). While APCI started to be used in gas chromatography-mass spectrometry (GC–MS) in 1970s, GC-APCI-MS was not widely used until recently. As a soft ionization technique, APCI provides highly diagnostic molecular ions, which is favored for the wide-scope screening. With the capability of tandem mass spectrometry (MS/MS), GC-APCI-MS methods with high sensitivity and selectivity have been developed and applied in the analysis of persistent organic pollutants (POPs) in environment and biological samples at trace levels. The present review introduces the history of the APCI source, with emphasis on mechanisms of ionization processes under the positive and negative ionization modes. Comparison between GC-APCI-MS and GC–MS with traditional electron ionization (EI) and chemical ionization (CI) are provided and discussed for selectivity, sensitivity and stability for the analyses of POPs. Previous studies found that the GC-APCI-MS methods provided limits of detection (LODs) around 10–100 times lower than other methods. An overview of GC-APCI-MS applications is given with the discussions on the advantages and drawbacks of various analytical methods applied for the analyses of POPs.     

A routine accredited method for the analysis of polychlorinated biphenyls,organochlorine pesticides,chlorobenzenes and screening of other halogenated organics in soil,sediment and sludge by GCxGC-μECD

The analysis of persistent organic pollutants is a real challenge due to the large number of compounds with varying chemical and physical properties. Gas chromatography with electron capture detection or mass spectrometry has been the method of choice for the past 50 years. Comprehensive two-dimensional gas chromatography (GCxGC) coupled with micro-electron capture detector (μECD) is a new method that can analyze polychlorinated biphenyls (PCBs), organochlorine pesticides (OCs) and chlorobenzenes (CBz) in a single analytical run with enhanced selectivity and sensitivity over single column methods and can also be used to screen for other halogenated organics in environmental samples. An accredited routine method using commercially available LECO GCxGC-μECD and a column combination DB-1 × Rtx-PCB has been developed to analyse PCBs/OCs/CBz in soils, sediments and sludges. The method provides quantification of Aroclors and Aroclor mixtures to within 15% of target values and sub-nanogrammes per gramme detection limits.