Seasonal variation and chemical composition of particulate matter: A study by XPS, ICP-AES and sequential microanalysis using Raman with SEM/EDS

During the winter period (January–March 2016), the total suspended particles (TSP) and particulate matter smaller than 2.5 μm (PM_2.5) were characterized by the application of various analytical techniques in four zones of the Metropolitan Area of Monterrey in Mexico. To evaluate the seasonal variation of some elements in the particulate matter, the results of this study were compared with those obtained during the summer season (July–September 2015). The speciation of the C_1s signal by X-ray photoelectron spectroscopy revealed the contribution of aromatic and aliphatic hydrocarbons as the main components in both seasons. Conversely, carboxylic groups associated with biogenic emissions were detected only in winter. The percentages of SO₄^2 ? ions were lower in winter, possibly caused by the decrease in the solar radiation, and relative humidity recorded. The results of the ICP analysis revealed that Fe, Zn and Cu were the most abundant metals in both TSP and PM_2.5 in the two seasons. There were significant seasonal variations for concentrations of As, Ni and Zn in the urban area and for Fe, As, Cd, Ni and Zn in the industrial zone. This was attributed to the greater burning of fuels as well as to an increase in vehicular traffic, the effect of thermal inversion and changes in some meteorological parameters. The results of the sequential microanalysis by Raman spectroscopy and SEM/EDS allowed observation of deposits of carbonaceous material on the particles and to perform the speciation of particles rich in Fe and Pb, which helped infer their possible emission sources.     

CeO2负载型双金属Pd/Fe催化还原四氯化碳的实验研究

实验采用共沉淀法制得CeO_2负载型双金属Pd/Fe催化剂,并对催化剂的结构特征进行了X射线衍射(XRD)和扫描电子显微镜(SEM)分析.使用负载型双金属催化剂对四氯化碳进行还原脱氯研究,探究了温度、溶液初始pH值、催化剂投加量及不同钯载率对四氯化碳脱氯的影响;对比了不同催化剂包括纳米零价铁、纳米钯铁双金属和CeO_2负载型双金属Pd/Fe对四氯化碳的脱氯效果.实验结果表明负载型双金属催化剂在温度为40℃,溶液初始pH为6.5,催化剂投加量为0.4 g·L-1,钯载率为0.5%的条件下,对初始浓度为5 mg·L-1的四氯化碳的去除率高达99.88%.在相同的反应条件下,纳米零价铁和纳米钯铁双金属对四氯化碳的脱氯率分别为58.25%、87.94%.此外,对四氯化碳的脱氯机制进行了探讨.     

纳米乳化油强化硝酸盐反硝化产气变化研究

为探究纳米乳化油原位修复硝酸盐污染地下水过程中产气对含水介质渗透性的影响,以硝酸盐为目标污染物,采用活性污泥滤液接种,分别以纳米乳化油、吐温80和司盘80为碳源开展硝酸盐降解批实验研究,探讨和评估硝酸盐降解及降解过程中的产气情况.结果显示,纳米乳化油、吐温80和司盘80均能促进硝氮的降解,在实验的100d内,共完成7个周期硝酸盐氮的有效去除,总去除率分别为79.5%、63.8%和68.8%.在硝酸盐氮降解过程中,受厌氧发酵和反硝化作用的影响,各反应体系中均有气体生成,只有活性污泥反应体系中主要产气成分是CO₂,未加碳源和分别加3种碳源的4个反应体系（都添加活性污泥和硝酸盐）中主要产气成分是CO₂、N₂.其中,添加纳米乳化油的反应体系U型管产气量最大,为47.73mL;受碳源厌氧发酵的影响,添加司盘80反应体系总产气量最大,为205.34mL.纳米乳化油反应体系次之,吐温80反应体系最小.根据三氮的变化,结合纳米乳化油反应体系理论与实际产气对比显示,在纳米乳化油强化硝酸盐反硝化过程中,18.8%纳米乳化油厌氧发酵产生CO₂,95.4%硝氮反硝化生成N₂.     

经手口途径摄入室内含PAHs灰尘颗粒的致癌风险评价

为了探究经手口途径摄入被PAHs污染室内灰尘的致癌风险,构建了居民经手口途径摄入被污染室内灰尘颗粒的概率风险模型,运用蒙特卡罗模拟方法评价了中国上海地区居民由PAHs引起的致癌风险,分析了致癌风险的主要来源及手口途径中各参数的重要程度。结果表明:幼儿和儿童所承受的风险最大,婴儿和成年人次之,青少年和老年人较小;对于致癌风险,幼儿和儿童超过10-6的概率都为80%,但超过10-4的概率都小于5%,婴儿和成年人超过10-6的概率都为50%,但婴儿超过10-4的概率小于5%,成年人的小于0.1%,青少年和老年人超过10-6的概率分别为10%和15%,不会高于10-4;室内硬表面灰尘引起的致癌风险远大于软表面灰尘引起的致癌风险;与致癌风险相关性最大的因素为灰尘颗粒中PAHs的等效斜率、灰尘在室内软硬表面的浓度、手到口途径发生的频率和颗粒物从手掌皮肤表面到口腔的转移率。     

HRT对瓷粒BAF处理生活污水效能的影响

通过实验室模型试验研究了瓷粒曝气生物滤池处理生活污水的效能,分析了在气水比一定的条件下,水力停留时间(HRT)变化对曝气生物滤池处理效能及运行特性的影响规律。考察了不同HRT运行下,COD、NH4+-N、NO2--N、NO3--N、TN、SS等指标的变化,结果表明,当进水COD为280～320mg/L,气水比为3:1,HRT为10h的条件下,处理效果最好,其中COD、NH4+-N、TN、SS的平均去除率分别为92.6%、97.8%、34.7%、84.2%。当HRT逐渐降低时,以上指标的去除效果都有所下降,但去除效能的下降与HRT的降低不呈线性关系。当HRT降至3h,去除效能有一定程度的上升,COD、NH4+-N、TN、SS的去除率有所增加。     

2007年春节期间北京大气颗粒物中多环芳烃的污染特征

利用大流量颗粒物采样器分昼夜采集了2007年春节前后大气气溶胶中PM10和PM2.5样品,并采用气相色谱-质谱技术对PM2 5样品中的多环芳烃进行了检测.春节期间大气颗粒物中PM10和PM2 5夜间平均质量浓度为232 ug·m-3和132 ug·m-3,分别高于白天的PM10(194ug·m-3)和PM2.5(107ug·m-3);除夕后颗粒物日平均质量浓度为252.3 ug·m-3(PM10)和123.8ug·m-3 (PM2.5),分别高于除夕前的166.7 ug·m-3(PM10)和106.8 ug·m-3(PM2.5);同时夜间PM2.5中多17种多环芳烃(PAHs)的总浓度都高于相应白天的总浓度,且除夕前多环芳烃日均总浓度为95.9 ng·m-3,高于除夕后的58.9 ng·m-3.结果表明,除了受一定的气象条件的影响外,大量燃放烟花爆竹会对大气颗粒物浓度有影响.但对大气中的多环芳烃影响不大,而春节期间工业及交通污染排放的减少削减了排放到大气中的PAHs.根据荧蒽/芘等比值指标判别北京PAHs主要以燃煤为主、交通为次的混合局地源污染.     

Characterization of organic matter in total suspended particles by thermodesorption and pyrolysis-gas chromatography-mass spectrometry

The organic matter in tropospheric aerosol plays an important role in atmospheric physical and chemical processes. The bulk of organic matter, representing a significant proportion of the total suspended particulate (TSP) mass, is bound to polymeric material whose structure and properties are largely unknown. Here we used thermodesorption gas chromatography/mass spectrometry (Td- GC/MS) to study organic compounds of low molecular mass and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) to characterize the chemical structure of macromolecules in TSP samples collected in di erent seasons from di erent sites in Guangzhou. n-Alkanes, fatty acids and nitriles were the predominant compounds in the thermodesorption products, whereas aromatics, fatty acids, nitriles and n-alkanes/alkenes were the major compounds in the pyrolysates. The results indicated that aromatics were main units in macromolecules. The fatty acids and nitriles formed from carboxylic ammonium salts were detected in both thermodesorption products and pyrolysates at a certain concentration, indicating the importance of these compounds in TSP formation. The TSP source mainly determined the occurrence of compounds in samples from urban, suburban and forest sites, whereas the TSP source and formation process maybe controlled the seasonal variation in compounds detected. High levels of nitriles in summer samples from suburban and forest sites coincide with the release of ammonium from the land and of fatty acids from vegetation at these sites.     

基于稳定同位素示踪的流域颗粒有机物质来源辨析

为有效控制流域水质污染,保证饮用水水源的水质安全,通过采集和测定流域内土壤、植物以及河流断面水体悬浮颗粒有机质(POM)在枯水期和丰水期的碳、氮稳定同位素值和C/N比值,对石头口门水库汇水流域水体POM的来源进行研究.结果表明,水体中POM主要来源于土壤有机质,其贡献为69.2%,藻类等大型水生生物和浮游植物的贡献分别为23.1%和7.7%.流域水体中POM的来源存在时空差异.丰水期,浮游植物和藻类等大型水生植物的贡献均为15.4%,而枯水期后者的贡献提高到了30.8%.水体POM主要来源于双阳河和饮马河下游的土壤有机质,说明该区域土壤侵蚀较重,易发生非点源污染;岔路河和饮马河上游支流小黄河,水体POM以浮游植物的贡献占主导,其贡献分别为86.3%和94.8%,这些区域侵蚀较弱,非点源污染发生的风险小;大中型水库区域的POM主要由藻类等大型水生植物贡献,表明悬浮颗粒物在进入水库后可能发生了明显沉积.     

上海市大气颗粒物中水溶性离子的粒径分布特征

分析了上海市嘉定区不同粒径的大气颗粒物中9种水溶性离子(SO42-、NO3-、NH4+、K+、Na+、Cl-、Ca2+、Mg2+、F-)的分布特征.结果显示,SO42-、NO3-和NH4+含量很高,占9种离子总和的65%～81%.颗粒物的C/A值平均为1.08,说明颗粒物呈中性,略偏碱,这可能与缺少碳酸根等的测定有关.1.5μm颗粒物中的离子占所有粒径段离子的52%～87%,表明离子主要集中在细颗粒物中.NH4+、K+呈单峰分布,峰值出现在0.95μm的颗粒段;SO42-、NO3-、Ca2+、Cl-呈双峰分布,峰值分别出现在0.95μm和3.0～7.2μm的粒径段,其中SO42-、NO3-的较高峰出现在0.95μm的细颗粒段,Ca2+的较高峰出现在3.0μm的颗粒段,Cl-则两峰高度相当;既有双峰分布又有单峰分布的离子是Na+、Mg2+和F-,3种离子的较高峰出现在3.0μm的颗粒段.离子粒径分布与采样期间的气象条件、离子的形成机制和来源有关.     

2007年春节期间北京大气细粒子中正构烷烃的污染特征

利用大流量颗粒物采样器分昼夜采集了2007年春节前后大气气溶胶中PM_2.5样品,并采用气相色谱-质谱技术对PM_2.5样品中的正构烷烃进行了检测和分析.结果表明,春节期间大气细粒子平均浓度全部超过WHO阈值,且夜间平均浓度要高于白天.细粒子中检测出C₁₀～C₃₃的正构烷烃,总浓度为201.7～2 715.6　ng·m^-3,夜间正构烷烃的平均总浓度（943.5 ng·m^-3）要高于白天(581.1 ng·m^-3）,除夕前的平均总浓度（1025.5 ng·m^-3）要高于除夕后（536.6 ng·m^-3）.主峰碳为23、 24和25,CPI值为0.9～1.4,平均为1.15,表明春节期间北京大气细粒子中的正构烷烃主要由化石燃料的不完全燃烧产生,%WaxC_n的结果表明生物源对气溶胶中正构烷烃的贡献率为8.5%～47%.