成都地区大气颗粒物中复杂有机物的色谱-质谱分析

〕本文报道了应用气相色谱和气相色谱-质谱联用法对成都地区大气颗粒物中复杂有机物的分析结果。实际分析中共鉴定出77种有机物,首次在成都地区大气颗粒物中发现含有烟碱这一新的污染物。同时对苯并[a]等28种主要污染物做了定量测定。结果表明,成都大气中的有机污染状况非常严重,急待采取有力措施加以改善。     

大气颗粒物中棕色碳的化学组成、来源和生成机制

大气颗粒物中棕色碳(BrC)在近紫外波段具有强吸光性,并因其显著的气候效应被广泛关注。BrC组成、来源、演变和光学性质的不确定性是造成气候模型估算气溶胶辐射强迫不确定性的重要因素。本文综述了大气颗粒物中BrC的化学组成、来源和生成机制,聚焦分子水平上BrC组成、二次生成机制和吸光间的关联。大气颗粒物中BrC的主要类别包括有机溶剂(甲醇)提取的碳质组分、水溶性有机碳及类腐殖质; 分子水平上,硝基芳香烃和含氮杂环有机物是BrC的主要发色团。BrC的来源包括生物质等不完全燃烧一次排放和挥发性有机物氧化二次生成; 二次生成途径主要包括人为源芳香烃氧化生成硝基芳香烃等含氮组分、羰基化合物与铵/胺反应生成含氮杂环组分或低聚物。前体物和反应条件影响二次生成BrC的组成和吸光性质; BrC在大气传输过程中还会发生“光漂白”现象。在分子水平上识别和阐明BrC的发色团、二次生成机制及其演变过程是未来该领域的重点研究方向。     

大气二次细颗粒物形成机理的前沿研究

大气二次颗粒物是影响大气辐射强迫和全球气候变化最不确定的因素之一.本文总结了大气二次细颗粒物的形成机制以及吸湿增长因子的研究进展.近年来,OH·、NO3·和O3光化学氧化形成二次细颗粒物的机制较为清晰,海盐和大气矿尘表面多相反应形成硫酸盐和硝酸盐等二次无机细颗粒物的研究取得可喜进展,尤其是发现海盐和大气矿尘混合物完全不同于单组分的多相反应机制.然而,二次有机颗粒物形成过程中能够鉴定出的有机组分很少,多相酸催化对形成二次颗粒物的促进作用尚未完全确定,多组分混合大气颗粒物的吸湿增长特性亦需进一步深入研究.     

柴胡中柴胡皂甙a的超声辅助溶剂提取

以溶剂提取法为基础,以超声波为辅助手段,对柴胡中的有效成分进行了提取.通过对提取液中柴胡皂甙a量的测定,研究了超声功率、提取温度、提取时间和样品浸渍时间等条件对提取效果的影响,优选出超声辅助溶剂提取的最佳条件为超声功率50%、提取温度50 ℃、提取时间20 min、样品浸渍时间24 h.实验结果表明,超声辅助溶剂提取比普通的溶剂提取具有更高的提取效率.     

~(13)C固体核磁共振技术检测PM_(2.5)中的总有机碳质组分

建立了13C固体核磁共振技术检测PM2.5中总有机碳质组分的分析方法。针对大气气溶胶中有机质组分的复杂性,探索出较为快速检测PM2.5中总有机质组分的核磁共振分析方法,使样品无需进行繁琐的前处理即可获得可靠的化学结构信息。利用该方法获得了太原、新乡、广州冬季PM2.5样品中总有机物的化学结构信息。结果表明,该方法操作简单,检测较为快速,准确度较高,可以满足大气气溶胶总有机成分的检测要求。     

生物油中固体颗粒物的特性分析

利用电感耦合等离子体发射光谱、红外光谱分析和X射线衍射对不同固体颗粒物样品的特性进行了研究。结果表明,生物油中的固体颗粒物主要由焦炭颗粒、灰分和少量高分子有机物组成,其中,灰分主要包括多种金属元素和一定量SiO₂,有机物主要是具有木质素结构的低聚物。不同热解工艺的固体颗粒物样品特性也不同。循环流化床工艺制取的生物油中固体颗粒物含量较高。此外,固体颗粒物样品中的金属元素含量受到热解原料种类的影响。     

自然水体悬浮颗粒物中主要化学组分对铅、铜的吸附作用——实验室模拟吸附特征与水环境中富集特征的比较

利用主要组分萃取-吸附-统计分析方法研究了自然水体悬浮颗粒物样品中主要化学组分对铅、铜的吸附特征, 并采用天然悬浮颗粒物样品直接萃取的方法研究了实际水环境中悬浮颗粒物样品各组分对重金属的富集特征, 通过二者对比进一步研究了悬浮颗粒物中主要化学组分在铅、铜吸附中的作用. 结果表明, 悬浮颗粒物样品中各组分的吸附特征与富集特征具有较好的可比性, 铅主要与颗粒物中的铁氧化物相结合, 铜则主要与有机质相结合.     

大气颗粒物中有机污染物分析技术研究进展

对颗粒物中常见有机污染物组成、来源及其分析技术进行总结。介绍了常见有机污染物的滤膜采样技术、前处理技术(溶剂萃取和热脱附)和色谱检测技术及所存在的问题。热脱附气相色谱–质谱联用技术在同时测定大气颗粒物中多环芳烃、正构烷烃等半挥发有机物方面具有明显优势。     

大气颗粒物中总碳含量的测量不确定度评定

分析了元素分析仪测定大气颗粒物中碳质组分的测量不确定度来源,对总碳含量的测量不确定度进行了评估。测定咖啡碱标准样品中的碳含量,称样量为1 500~2 500μg时,测定结果为(49.27±0.26)%;测定大气颗粒物样品中的总碳含量,样品面积为3.14 cm2时,测定结果为(106±3)μg/cm2。     

大气颗粒物中有机硝酸酯的研究进展

有机硝酸酯是大气中挥发性有机物与自由基反应的产物,半挥发性的气相有机硝酸酯可以通过氧化反应或气粒分配作用进入颗粒相,是二次有机物的一个重要组成部分,逐渐引起大气化学研究者的广泛关注。颗粒相有机硝酸酯具有分子种类众多、理化性质复杂的特点,其全组分的测定有较高的难度,故目前开展的研究还较为有限。基于近年来国内外相关研究,本文对大气颗粒物中有机硝酸酯的形成机制、测定技术和估算方法进行了总结。随着测定技术的不断发展,外场观测已成为颗粒相有机硝酸酯的主要研究方法。热解析管激光诱导荧光系统(TD-LIF)和气溶胶质谱(AMS)为颗粒相有机硝酸酯的总量估算提供了方法,同时其较高时间分辨率的测定方法也为研究有机硝酸酯的大气行为提供更多信息。化学电离源质谱(CIMS)可以提供颗粒相有机硝酸酯的分子信息,有望在外场观测中得到广泛运用。在未来研究中,将外场观测研究、模型模拟和烟雾箱模拟实验相互结合,以实现对颗粒相有机硝酸酯的前体物追踪、大气化学过程的深入了解,为揭示大气颗粒物中有机硝酸酯的生成机制提供新的方向。     

Recent advances in metal‐organic frameworks and covalent organic frameworks for sample preparation and chromatographic analysis

In the field of analytical chemistry, sample preparation and chromatographic separation are two core procedures. The means by which to improve the sensitivity, selectivity and detection limit of a method have become a topic of great interest. Recently, porous organic frameworks, such as metal‐organic frameworks (MOFs) and covalent organic frameworks (COFs), have been widely used in this research area because of their special features, and different methods have been developed. This review summarizes the applications of MOFs and COFs in sample preparation and chromatographic stationary phases. The MOF‐ or COF‐based solid‐phase extraction (SPE), solid‐phase microextraction (SPME), gas chromatography (GC), high‐performance liquid chromatography (HPLC) and capillary electrochromatography (CEC) methods are described. The excellent properties of MOFs and COFs have resulted in intense interest in exploring their performance and mechanisms for sample preparation and chromatographic separation.     

有机聚合物整体柱的改性与应用进展

有机聚合物整体柱具有制备简单、易于改性和通透性好的优点,不仅可作为微柱色谱分离分析的固定相,而且可用作样品纯化富集的载体,广泛应用于基体复杂的生化样品分析领域.该文综述了近年来有机聚合物整体柱的研究进展,重点介绍了其制备方法、改性技术及在生化样品预处理领域的研究动态.针对其制备方法,从制备过程、制备原料(单体、交联剂、...     

植物激素样品前处理方法的研究进展

植物激素是植物中一类含量很低,却对植物生长发育等生命过程起重要调控作用的有机化合物。近年色谱/质谱联用技术不断发展,已成为植物激素分析的常用方法,而样品前处理则是色谱分析过程中的一个关键环节,所以高选择性和高回收率的前处理方法对于植物激素的分析至关重要。根据植物激素的化学性质,本文将其分为酸碱性植物激素、油菜素甾醇、植物多肽3类,并对相应的前处理方法加以综述,特别是近年来发展起来的新方法。内容包括前处理方法的原理、装置、萃取材料以及衍生试剂等,相关内容主要围绕本研究组的痕量植物激素研究工作展开,最后对研究趋势做了简短展望。     

Characterization of natural organic colorants in historical and art objects by high‐performance liquid chromatography

High‐performance liquid chromatography plays an important role in analysis of historical organic colorants. A number of papers have been published in this field over the last 30 years. Classification of the most commonly used natural dyes and an overview of high‐performance liquid chromatography methods with main focus on recent works (2008 to the beginning of 2014) are provided. The review deals with an entire analytical protocol covering sample preparation, chromatographic separation, and suitable detection (UV/visible and fluorescent spectroscopy and mass spectrometric techniques). High‐performance liquid chromatography has been successfully used in the complete characterization of some organic dyestuffs present in historical and art objects. The possibilities and difficulties for identification of natural sources of historical colorants are also discussed.     

Large volume injection techniques in capillary gas chromatography

Large volume injection (LVI) is a prerequisite of modern gas chromatographic (GC) analysis, especially when trace sample components have to be determined at very low concentration levels. Injection of larger than usual sample volumes increases sensitivity and/or reduces (or even eliminates) the need for extract concentration steps. Also, an LVI technique can serve as an interface for on-line connection of GC with a sample preparation step or with liquid chromatography. This article reviews the currently available LVI techniques, including basic approaches to their optimization and important real-world applications. The most common LVI methods are on-column and programmed temperature vaporization (PTV) in solvent split mode. Newer techniques discussed in this article include direct sample introduction (DSI), splitless overflow, at-column, and "through oven transfer adsorption desorption" (TOTAD).     

An international round-robin study for the analysis of particulate semi-volatile organics by thermal desorption gas chromatography mass spectrometry

Thermal desorption gas chromatography mass spectrometry (TD-GC/MS) is becoming more commonly used for the quantification and identification of organic compounds in particulate matter (PM), including ambient and source PM such as diesel particulate matter (DPM). It has been proven as an alternative to the traditional solvent extraction (SE) method and liquid injection gas chromatograph mass spectrometry (LI-GC/MS). However, little information is available on how different types of TD-GC/MS systems compare to each other for analysis of real-world PM samples or to direct LI-GC/MS for analysis of PM components in a test solution. To address this, CanmetENERGY Characterization Laboratory initiated a round robin with the participation of 10 laboratories worldwide. Three sample types were analysed: (i) a test solution with a suite of pure compounds commonly found in PM, analysed by TD-GC/MS and LI-GC/MS; (ii) a DPM sample, analysed by TD-GC/MS and SE; and (iii) an ambient PM sample, analysed by TD-GC/MS. The first part of the study showed good overall performance and comparability between the different TD-GC/MS systems and LI-GC/MS method for the analysis of PM components in a test solution, with some variability of results due to system types and parameters used, concentration of calibration standards, and whether or not an internal standards was used. The analysis of the DPM sample showed greater variability between laboratories and methods as many PM components were present near the detection limit and matrix effects particularly affected the TD-GC/MS analysis of heavier n-alkanes. In the last part of the study, for the analysis of an ambient PM sample by TD-GC/MS, the analysis of variance showed good comparison between labs for polycyclic aromatic hydrocarbons (94% non-significant), but slightly lower for n-alkanes (68%) and biomarkers (57%).     

Sample preparation for organic acids in biological fluids

A review of sample preparation methods for organic acids in biological fluids, in particular serum and urine, is presented. It covers techniques on organic acid determination without sample preparation, release of organic acids from binding locations, removal of proteins by protein precipitation and ultrafiltration, isolation of the organic acids by liquid-liquid and liquid-solid extraction, purification of the extract, derivatization and pre-fractionation. The various alternative sample preparation steps are compared and critically discussed. Examples of applications including profile analysis of organic acids by gas chromatography (GC), determination of particular organic acids by GC or liquid chromatography and determination of fatty acids as a distinct chemical class of acids demonstrate that the kind of sample preparation chosen depends strongly on the analytical aims.     

Experimental study on solvent-less sample preparation methods: Membrane extraction with a sorbent interface, thermal membrane desorption application and purge-and-trap

Different solvent-free sample preparation techniques for the enrichment of volatile and semivolatile organic compounds from aqueous samples for subsequent gas chromatographic separation and detection are compared. The methods under study are purge-and-trap, membrane extraction with a sorbent interface in two different configurations, and thermal membrane desorption application. The study has been performed with polar as well as with non-polar compounds in respect to sampling yield, enrichment, repeatability and analysis cycle rate. All experiments have been performed with a mobile GC–MS system.     

Sample preparation methods in the analysis of pesticide residues in baby food with subsequent chromatographic determination

Pesticides are widely utilized at various stages of cultivation and during postharvest storage to protect plants against a range of pests and/or to provide quality preservation. Reliable confirmatory methods are required to monitor pesticide residues in baby foods and to ensure the safety of baby food supply. This review covers methods in which pesticide residues have been determined in baby food by the use of a wide range of chromatographic techniques after various sample preparation steps. The main attention is paid to the evaluation and improvement of sample extraction and clean-up methods (liquid extraction, solid-phase extraction (SPE), dispersive SPE (DSPE), microextraction procedures, matrix solid-phase dispersion (MSPD) and supercritical fluid extraction (SFE)) considering low concentration levels of pesticide residues in baby food resulting from stringent European Union (EU) legislation. Instrumental aspects together with the matrix effects significantly contributing to the most important parameters considered in pesticide residues analysis of baby food--limits of detection (LODs) and limits of quantification (LOQs) were included within the scope of this overview. Paper involves also monitoring studies.     

Analytical approaches for arsenic determination in air: A critical review

This review describes the different steps involved in the determination of arsenic in air, considering the particulate matter (PM) and the gaseous phase. The review focuses on sampling, sample preparation and instrumental analytical techniques for both total arsenic determination and speciation analysis. The origin, concentration and legislation concerning arsenic in ambient air are also considered. The review intends to describe the procedures for sample collection of total suspended particles (TSP) or particles with a certain diameter expressed in microns (e.g. PM10 and PM2.5), or the collection of the gaseous phase containing gaseous arsenic species. Sample digestion of the collecting media for PM is described, indicating proposed and established procedures that use acids or mixtures of acids aided with different heating procedures. The detection techniques are summarized and compared (ICP-MS, ICP-OES and ET-AAS), as well those techniques capable of direct analysis of the solid sample (PIXE, INAA and XRF). The studies about speciation in PM are also discussed, considering the initial works that employed a cold trap in combination with atomic spectroscopy detectors, or the more recent studies based on chromatography (GC or HPLC) combined with atomic or mass detectors (AFS, ICP-MS and MS). Further trends and challenges about determination of As in air are also addressed.