南宁市一次污染过程大气颗粒物理化特性及来源

利用颗粒物粒径谱仪和单颗粒气溶胶质谱仪等,对南宁市2016年12月5~11日大气污染过程进行实时监测,分析颗粒物粒径分布特征、化学组分及其污染来源.结果表明,观测期间南宁市20 nm~10μm颗粒物数浓度粒径主要集中在23~395 nm之间,主峰值出现在100 nm左右.期间有3次新粒子生成现象,下午14:00~18:00有30 nm左右新粒子开始生成,晚20:00~次日06:00碰并长大到40~110 nm左右,3次新粒子生成过程受机动车尾气一次排放的污染影响.对污染期间细颗粒物化学成分在线溯源分析发现,污染期间有大量的二次反应颗粒物生成,判定颗粒物来源主要有生物质燃烧源、扬尘源和燃煤源,其中,远距离传输对生物质燃烧源有贡献.     

Single particle analysis of ambient aerosols in Shanghai during the World Exposition, 2010: two case studies

ATSI Model 3800 aerosol time-of-flight mass spectrometer (ATOFMS) was deployed for single-particle analysis in Shanghai during the World Exposition (EXPO), 2010. Measurements on two extreme cases: polluted day (1st May) and clean day (25th September) were compared to show how meteorological conditions affected the concentration and composition of ambient aerosols. Mass spectra of 90496 and 50407 particles were analyzed respectively during the two sampling periods. The ART-2a neural network algorithm was applied to sort the collected particles. Seven major classes of particles were obtained: dust, sea salt, industrial, biomass burning, organic carbon (OC), elementary carbon (EC), and NH₄-rich particles. Number concentration of ambient aerosols showed a strong anti-correlation with the boundary layer height variation. The external mixing states of aerosols were quite different during two sampling periods because of different air parcel trajectories. Number fraction of biomass burning particles (43.3%) during polluted episode was much higher than that (21.6%) of clean time. Air parcels from the East China Sea on clean day diluted local pollutant concentration and increased the portion of sea salt particle dramatically (13.3%). The large contribution of biomass burning particles in both cases might be an indication of a constant regional background of biomass burning emission. Mass spectrum analysis showed that chemical compositions and internal mixing states of almost all the particle types were more complicate during polluted episode compared with those observed in clean time. Strong nitrate signals in the mass spectra suggested that most of the particles collected on polluted day had gone through some aging processes before reaching the sampling site.     

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%。     

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.     

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.     

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.     

太湖西岸地表水中极性有机污染物非靶向筛查与生态风险评估

环境中新兴污染物层出不穷,已经成为当前环境研究的关键问题.为全面筛查太湖西岸武进和宜兴地区地表水中的潜在极性有机污染物,基于高效液相色谱和飞行时间质谱联用技术进行非靶向筛查,利用精确质量数、同位素分布和二级碎片信息进行质谱库匹配共识别出162个有机物,包括46种农药、34种药物、8种个人护理产品、27种添加剂、17种有机合成中间体和30种动植物代谢物或天然物质,其中45个有机物经过标准品验证.对42种污染物进行定量分析并对3种营养级模式生物物种进行生态风险评估,发现25种污染物具有中等风险以上,12种污染物具有高风险.非靶向筛查能够在无先验信息和标准品的情况下全面识别潜在未知污染物,不仅快速、准确和分析通量高,还能为后续生态风险评估提供重要的依据.     

气相分子吸收光谱法测定水中硫化物浓度不确定度评定

采用气相分子吸收光谱仪法测定水样中硫化物的浓度,对其不确定度来源进行分析、评估。结果表明,当水样浓度为3．42mg/L时,考虑测定过程的标准溶液的配制、曲线拟合、仪器测量重复性等因素对测定结果造成影响,测得硫化物的相对合成标准不确定0．13mg/L,其中最主要的分量是由硫化物标准溶液引起的测量不确定度。     

黑炭气溶胶质谱仪(SP-AMS)分析春季PM2.5中水溶性有机气溶胶

为探讨常州春季大气细颗粒物(PM_2.5)的化学组成及污染特征,于2017年3月1日～5月30日采集了84个有效样品,对其水溶性离子(WSIIs)、碳质组分(OC和EC)等常规组分进行了测定和分析,并采用黑炭-气溶胶质谱仪(SP-AMS)对水溶性有机气溶胶(WSOA)进行了分析.结果表明,采样期间PM_2.5的日均质量浓度为101. 97μg·m^-3,超标(环境空气质量标准二级标准)率达73. 8%,以轻度、中度和重度污染为主,分别占总天数的39. 3%、21. 4%和13. 1%. WSIIs约占PM_2.5的39. 86%,其中二次离子(SO₄^2-、NH₄⁺和NO₃^-)占WSIIs的81. 85%,阴阳离子电荷平衡的线性拟合直线的斜率(AE/CE)大于1(1. 09),表明PM_2.5偏弱酸性. OC/EC比值为2. 53,说明受二次转化的影响. SP...     

Effect of air masses motion on the rapid change of aerosols in marine atmosphere

The impact of air masses motion on marine aerosol properties was investigated using an on-board single particle mass spectrometer(SPAMS) deployed for the determination of single particle size resolved chemical composition over Southeast China Sea. Two aerosol blooms(E1 and E2) were observed during the cruise. High average particle number count occurred in E1(7320), followed by E2(5850), which was more than 100–150 times of the average particle number count during normal periods. Particles were classified as four major sources, including continental source, shipping source, marine source, and transport source based on the mass spectral similarity. Transport source was identified as those particles with high particle number count occurred only during aerosol bloom period. Three sub-types of EC-Ca, OC-Ca, and Al-rich were classified as transport source.EC-Ca was the dominant particles of the transport source, accounting for more than 70%of the total particles in aerosol bloom events. A uni-modal size distribution in the size range of 0.1–2.0 μm was observed during normal period, while a bimodal distribution with a tiny mode(0.3 μm) and a coarse mode between 0.4 and 0.6 μm was present during aerosol bloom. The variation of aerosol source is consistent with air masses back trajectories, for the reason that most of the long-range air trajectories are from the ocean,while short air trajectories originate in the continental regions, which means that air masses have a significant impact on the aerosol physical–chemical properties along their tracks.