单光子/光电子在线质谱实时分析聚氯乙烯热分解/燃烧产物

实验室研制了低能光电子磁场增强电离(MEPEI)和单光子电离(SPI)复合电离源,该电离源具有电离化合物范围宽、碎片离子少、质谱图简单等优点,结合飞行时间质谱(TOF-MS)实现了聚氯乙烯(PVC)热分解/燃烧产物的在线分析.针对不同的目标化合物,MEPEI/SPI复合电离源通过调节电离区电场强度,可以快速在SPI和SPI-MEPEI之间切换.PVC热分解/燃烧产物中电离能大于光子能量(10.60 eV)的HCl和CO2(12.74 eV、13.77 eV)利用MEPEI模式电离;而烯烃、二氯乙烯、苯系物、氯苯、苯乙烯、茚满及萘系物等可通过SPI-MEPEI复合模式电离.通过实时监测PVC主要燃烧产物的信号强度随温度的变化趋势可推断出,PVC燃烧产物主要是通过两种机制生成:①250～370℃时,PVC发生脱氯及分子内环化反应,产生大量的HCl、苯和萘;②380～510℃时,PVC发生分子间交联反应,生成烷基芳烃,如甲苯和二甲苯/乙苯等.实验结果表明,SPI/SPI-MEPEI复合离子源TOF-MS分析速度快,应用范围广,在在线分析中具有广泛的应用前景.     

Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants

The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.     

基于单颗粒质谱信息气溶胶分类方法的研究进展

气溶胶质谱仪在对气溶胶颗粒的监测过程中会产生大量单颗粒的化学成分和粒径信息,基于这些质谱数据能够推测颗粒的来源。而对气溶胶来源的分析,很大程度上是由颗粒的种类决定的,故对海量数据的分类就成为不可忽略的步骤。针对气溶胶质谱仪采集到的数据,概述了用于气溶胶分类的多种方法的理论核心、分类步骤及各自的优缺点等。据此可为今后气溶胶分类方法的研究提供建设性意见。     

原子荧光光谱仪测定底泥中砷含量的不确定度评定

介绍了原子荧光光谱仪测定底泥中砷含量的不确定度评定方法,分析和识别测量过程中不确定度的来源,较为全面地评定了测量不确定度。根据最小二乘法拟合计算工作曲线的标准不确定度,采用极差法评定测量次数较少时引起的标准不确定度。     

Impacts of converting from leaded to unleaded gasoline on ambient lead concentrations in Jakarta metropolitan area

Total suspended particulate mater （TSP） concentrations were monitored for one year from July 2000 and for one year from April 2003 in Jakarta City. Thirteen elemental TSP components, aluminum （Al）, sodium （Na）, iron （Fe）, lead （Pb）, potassium （K）, zinc （Zn）, titanium （Ti）, manganese （Mn）, bromine （Br）, copper （Cu）, chromium （Cr）, nickel （Ni）, and vanadium （V） were analyzed by a sequential X-ray fluorescence spectrometer. Al, Na, Fe, K, and Pb were major components at most of the sampling locations in 2000. However, only Pb in 2003 dramatically decreased to one tenth. The phase-out of leaded gasoline began on July 1, 2001 in Jakarta City and lead content in gasoline decreased to one tenth, too. The decrease in Pb concentration was a result of the phase-out of leaded gasoline, as lead emissions mainly are exhaust gas from vehicles.     

锶盐废渣含硫状态分析及硫含量的测定

锶盐废渣中硫的状态及含量不同其作用大不相同,有的呈现活性导致膨胀破坏,而有的则表现为惰性,因此有必要了解硫的存在状态及含量。分析表明锶盐废渣中硫主要以硫酸盐硫(SO3)和硫化物硫(S2-)两种形式存在。选择硫酸钡重量法和碘量法进行化学测定,然后用X-射线能谱仪进行元素定性分析;并将化学分析和仪器测定两种方法进行对比。结果表明,X-射线能谱法可以快捷、方便地探测锶渣所含各种元素,但不能确定元素的价态;化学分析方法可得到相对准确的元素含量;用硫酸钡重量法和碘量法联合测定锶渣中的硫含量,与X-射线能谱法相比,偏差仅为0.37%。     

便携式GC/MS热脱附法直接测定环境空气中挥发性有机物

采用便携式气相色谱/质谱联用热脱附法直接测定环境空气中的挥发性有机物,优化了试验条件。方法在5×10-9~100×10-9范围内线性良好,39种化合物的检出限为1.1μg/m3~19μg/m3,标准气体平行测定的RSD≤11.0%,回收率在80%~120%之间。     

Decay profile and metabolic pathways of quinalphos in water, soil and plants

The widespread occurrence of pesticide residues in different agricultural and food commodities has raised concern among the environmentalists and food chemists. In order to keep a proper track of these materials, studies on their decay profiles in the various segments of ecosystem under varying environmental conditions are needed. In view of this, the metabolites of quinalphos in water and soil under controlled conditions and in plants, namely tomato and radish in field conditions have been analysed and possible pathways suggested. In order to follow the decay of the pesticide, an HPLC procedure has been developed. Studies conducted in water at different temperatures, pH and organic content reveal that the persistence of the pesticide decreases with the increase in all the three variables. In the three different types of soils studied, the effect of pH is more or less apparent on a similar line. On an average a faster decay is observed in the case of plants than in water and soil. The decay profiles in all these cases follow first order kinetics. The metabolites were identified by GC-MS. The investigations reflect that degradation occurs through hydrolysis, S-oxidation, dealkylation and thiono-thiol rearrangement. The pathways seem to be complex and different metabolites were observed with the change in the matrix. Quinalphos oxon, O-ethyl-O-quinoxalin-2-yl phosphoric acid, 2-hydroxy quinoxaline and quinoxaline-2-thiol were observed in all the matrices. Results further indicate that the metabolites, 2-hydroxy quinoxaline and oxon, which are more toxic than parent compound, persist for a longer time.     

基于放射性碳分析的多环芳烃源解析:技术进展和准确性评估

化石燃料燃烧和生物质燃烧是污染物多环芳烃(polycyclic aromatic hydrocarbon,PAHs)的两大来源.放射性碳(14C)分析近年用于评估这两类源对环境中PAHs的相对贡献.此方法基于化石燃料和生物质的14C含量差异,即化石燃料不含14C,而生物质的14C浓度有一个较稳定值.14C的自然丰度极低(约10-12),因此检测PAHs这样的痕量污染物的14C含量一度极具挑战.1990年代中期,加速器质谱的技术突破使得对环境样品PAHs的14C分析具有实用价值.要准确测出PAHs的14C含量,须先从化学成分复杂的环境样品中分离出高纯度的PAHs.制备气相色谱因其出色的分离能力而成为目前环境样品PAHs14C分析必备的工具.本文意在简介基于14C分析的PAHs源解析的基本原理、技术进展,以及评估该方法获得的PAHs源解析结果的准确性.     

基于可疑筛查技术研究有机磷阻燃剂V6转化规律

运用Orbitrap高分辨质谱仪,评估了人体肝微粒体(HLM)代谢V6的转化规律.除5种已被报道过的O-脱烷基、氧化性去磷酸化和氧化脱氯产物外,首次发现了6种新型产物.基于其MS/MS质谱图,该6种代谢产物被鉴定为醛基和羧基产物.其中,5种代谢物生成量随孵育时间呈线性增加趋势,具有累积性.此外,推导的代谢途径表明,脱烷基化和羟基化代谢物进一步转化为次级代谢物,即醛和羧基代谢物.