La-Co-Fe-Cu/HZSM-5在尾气碳颗粒燃烧中的催化性能

采用柠檬酸络合低温浸渍法制备分子筛负载钙钛矿型复合氧化物催化剂。采用XRD、SEM和H2-TPR等手段对催化剂性能进行表征,并在微型固定床反应器中对催化剂进行活性评价。结果表明,在钙钛矿型复合氧化物中进行B位离子掺杂,可以改善催化活性,碳颗粒燃烧温度降低。在20%LaCoO3/HZSM-5催化剂中用铁离子部分取代钴离子可以改善碳颗粒的燃烧性能,取代量增加碳颗粒燃烧温度降低,但是生成CO2的选择性也降低,以20%LaCo0.2Fe0.8O3/HZSM-5为催化剂,Tig、Tm和Tf分别为256℃、399℃和403℃,但生成CO2的选择性只有72.5%。在20%LaCo1-xFexO3/HZSM-5中的钙钛矿型复合氧化物B位离子中加入铜离子后,在碳颗粒燃烧反应中生成CO2的选择性得到明显改善,Sco2提高10个单位以上。以20%LaCo0.2Fe0.6Cu0.2O3/HZSM-5为催化剂,在碳颗粒燃烧反应中生成CO2的选择性可以达到94.7%,Tig、Tm和Tf分别为242℃、427℃和445℃。     

Cu-K型低温碳烟氧化催化剂的合成及表征

柴油机排放中碳烟的低温氧化是近年来研究的热点.通过原位合成法制备Cu2K/Al2O3和CuK／Al2O3两种碳烟氧化催化剂,并采用低温氮吸附/脱附实验、X射线衍射、X射线光电子能谱、程序升温氧化对其结构进行系统表征,并用U碳模拟柴油机碳烟,研究其催化活性,评测其对柴油机排气中碳烟颗粒的净化效果.研究表明,Cu2K/Al...     

焦作市高新区冬季大气不同粒径颗粒物质量特征分析

用大流量冲击式分级采样器采集大气颗粒物样品,通过重量法求出不同粒径颗粒物的质量,研究不同粒径颗粒物的质量百分比.分析不同粒径颗粒物与风速、温度、湿度等气象条件的变化规律.结果表明:各级颗粒物整体与温度和风速呈负相关性,与湿度呈正相关性,且粒径小于2.1 μm的颗粒物与湿度相关性最大.大气颗粒物主要集中在2.1 μm以下...     

Compositions and sources of organic acids in fine particles (PM2.5) over the Pearl River Delta region, south China

Organic acids as important constituents of organic aerosols not only influence the aerosols' hygroscopic property, but also enhance the formation of new particles and secondary organic aerosols. This study reported organic acids including C14–C32fatty acids, C4–C9dicarboxylic acids and aromatic acids in PM2.5collected during winter 2009 at six typical urban, suburban and rural sites in the Pearl River Delta region. Averaged concentrations of C14–C32fatty acids, aromatic acids and C4– C9 dicarboxylic acids were 157, 72.5 and 50.7 ng/m3, respectively. They totally accounted for 1.7% of measured organic carbon. C20–C32fatty acids mainly deriving from higher plant wax showed the highest concentration at the upwind rural site with more vegetation around, while C14–C18fatty acids were more abundant at urban and suburban sites, and dicarboxylic acids and aromatic acids except 1,4-phthalic acid peaked at the downwind rural site. Succinic and azelaic acid were the most abundant among C4–C9dicarboxylic acids, and 1,2-phthalic and 1,4-phthalic acid were dominant aromatic acids. Dicarboxylic acids and aromatic acids exhibited significant mutual correlations except for 1,4-phthalic acid, which was probably primarily emitted from combustion of solid wastes containing polyethylene terephthalate plastics. Spatial patterns and correlations with typical source tracers suggested that C14–C32fatty acids were mainly primary while dicarboxylic and aromatic acids were largely secondary. Principal component analysis resolved six sources including biomass burning, natural higher plant wax, two mixed anthropogenic and two secondary sources; further multiple linear regression revealed their contributions to individual organic acids. It turned out that more than 70% of C14–C18fatty acids were attributed to anthropogenic sources, about 50%–85% of the C20–C32fatty acids were attributed to natural sources, 80%–95% of dicarboxylic acids and 1,2-phthalic acid were secondary in contrast with that 81% of 1,4-phthalic acid was primary.     

Characteristics of atmospheric particles and heavy metals in winter in Chang-Zhu-Tan city clusters, China

To understand the pollution characteristics of atmospheric particles and heavy metals in winter in Chang-Zhu-Tan city clusters, China, total suspended particulate(TSP) and PM10samples were collected in cities of Changsha, Zhuzhou and Xiangtan from December 2011 to January 2012, and heavy metals of Cd, Pb, Cr, and As were analyzed. It shows that the average TSP concentration in Changsha, Zhuzhou and Xiangtan were(183 ± 73),(201 ± 84) and(190 ± 66) μg/m3respectively, and the average PM10 were(171 ± 82),(178 ± 65) and(179 ± 55) μg/m3respectively. The lowest TSP and PM10concentrations occurred at the background Shaping site of Changsha. The average ratio of ρ(PM10)/ρ(TSP) was 91.9%, ranging from 81.3% to 98.9%. Concerning heavy metals, in TSP samples, the concentration of Cr, As, Cd and Pb were 28.8–56.5, 18.1–76.3, 3.9–26.1 and 148.0–460.9 ng/m3, respectively, while in PM10samples, were 16.4–42.1, 15.5–67.9, 3.3–22.2 and 127.9–389.3 ng/m3, respectively. The enrichment factor of Cd was the highest, followed by Pb and As, while that of Cr was the lowest.     

杭州灰霾天气超细颗粒浓度分布特征

利用快速迁移率粒径谱仪(FMPS)对杭州2013年12月6～11日连续灰霾天气和灰霾消退过程超细颗粒进行监测,分析颗粒物浓度变化和粒径谱分布特征及其与气象的相关性.结果表明,颗粒物日变化特征为夜晚数浓度较高,凌晨数浓度开始降低,08:00和18:00上下班高峰期出现一个小峰值,体现出明显的交通源峰值,表明交通排放对大气污染影响较大.灰霾天气下颗粒物最高数浓度达到8.0×104cm-3.粒径谱呈双峰分布,峰值粒径分别为15 nm和100 nm,粒径在100 nm附近的粒子占大多数,粒子以爱根核模态和积聚模态为主,平均数量中位径CMD(count medium diameter)为85.89 nm.而在灰霾消退过程,颗粒物数浓度降低,峰值粒径向小粒径演变,粒径在100 nm附近的粒子逐渐减少,核模态粒子增多,大于积聚模态,平均CMD为58.64 nm.气象因素中能见度和风力与数浓度主要呈负相关,相关系数R分别为-0.225和-0.229,相对湿度与数浓度正相关,相关系数R为0.271,冬季大气比较稳定,水平温度与数浓度的相关性较小.研究灰霾天气数浓度分布和气象因素的综合影响对其形成机制及控制有重要意义.     

模拟烹饪油烟的粒径分布与扩散

烹饪油烟颗粒物粒径分布与扩散特性研究有助于解析其对室内空气质量和居民健康的影响,采用电子低压撞击器(ELPI)实时监测了油烟机开启和关闭状态下,模拟烹饪油烟发生处和3 m外位置处,0.03~10μm范围内油烟颗粒数浓度和质量浓度随粒径分布.油烟颗粒主要以655 nm以下的细颗粒为主.油烟机能够显著降低室内油烟浓度,开启油烟机后,油烟发生处颗粒数浓度从2.8×106个·cm-3降低到2.3×105个·cm-3,PM2.5(空气动力学直径≤2.5μm的颗粒)质量浓度从85.9 mg·m-3降低到6.2 mg·m-3.油烟机对PM10的净化效率高于PM2.5.油烟迅速从发生处扩散到3 m外,无通风状态下,总颗粒数浓度衰减达65%,PM2.5质量浓度衰减达75%.计算流体动力学(CFD)模拟了油烟机对油烟PM2.5质量浓度场扩散分布影响.红外摄像仪监测了油烟温度场分布扩散,以扇形向外扩散,伴随着油烟温度梯度降低.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) to carbonaceous materials in a river floodplain soil

We report on sorption isotherm of phenanthrene (Phe) for river floodplain soil associated with carbonaceous materials, with particular attention being devoted to the natural loading of Phe. Our sorption experiments with original soil samples, size, and density sub-fractions showed that the light fraction had the highest sorption capacity comparable to low rank coals. In addition, the light fraction contributed most for the sorption of Phe in total soil samples. K_oc values for all fractions were in the same range, thus indicating that coal and coal-derived particles in all samples are responsible for the enhanced sorption for Phe. Sorption was strongly nonlinear and the combined partitioning and pore-filling model gave a better fit than the Freundlich sorption model. In addition, the spiked PAHs did not show the same behavior as the naturally aged ones, therefore the accessibility of indigenous background organic contaminants was reduced when coal and coal-derived particles are associated with the soils.     

Improvement of an efficient separation method for chemicals in diesel exhaust particles: analysis for nitrophenols

GOAL, SCOPE, AND BACKGROUND: Diesel exhaust is believed to consist of thousands of organic constituents and is a major cause of urban pollution. We recently reported that a systematic separation procedure involving successive solvent extractions, followed by repeated column chromatography, resulted in the isolation of vasodilatory active nitrophenols. These findings indicated that the estimation of the amount of nitrophenols in the environment is important to evaluate their effect on human health. The isolation procedure, however, involved successive solvent extractions followed by tedious, repeated chromatography, resulting in poor fractionation and in a significant loss of accuracy and reliability. Therefore, it was crucial to develop an alternative, efficient, and reliable analytical method. Here, we describe a facile and efficient acid-base extraction procedure for the analysis of nitrophenols. MATERIALS AND METHODS: Diesel exhaust particles (DEP) were collected from the exhaust of a 4JB1-type engine (ISUZU Automobile Co., Tokyo, Japan). Gas chromatography-mass spectrometry (GC-MS) analysis was performed with a GCMS-QP2010 instrument (Shimadzu, Kyoto, Japan). RESULTS: A solution of DEP in 1-butanol was extracted with aqueous NaOH to afford a nitrophenol-rich oily extract. The resulting oil was methylated with trimethylsilyldiazomethane and subsequently subjected to GC-MS analysis, revealing that 4-nitrophenol, 3-methyl-4-nitrophenol, 2-methyl-4-nitrophenol, and 4-nitro-3-phenylphenol were present in significantly higher concentrations than those reported previously. DISCUSSION: Simple acid-base extraction followed by the direct analysis of the resulting extract by GC-MS gave only broad peaks of nitrophenols with a poor detection limit, while the GC-MS analysis of the sample pretreated with (trimethylsilyl)diazomethane gave satisfactorily clear chromatograms with sharp peaks and with a significantly lowered detection limit (0.5 ng/ml, approximately 100 times). CONCLUSION: The present method involving an acid-base extraction, in situ derivatization, and GC-MS analysis has shown to be a simple, efficient, and reliable method for the isolation and identification of the chemical substances in DEP.     

Spatial & temporal variations of PM10 and particle number concentrations in urban air

The size of particles in urban air varies over four orders of magnitude (from 0.001 μm to 10 μm in diameter). In many cities only particle mass concentrations (PM10, i.e. particles <10 μm diameter) is measured. In this paper we analyze how differences in emissions, background concentrations and meteorology affect the temporal and spatial distribution of PM10 and total particle number concentrations (PNC) based on measurements and dispersion modeling in Stockholm, Sweden. PNC at densely trafficked kerbside locations are dominated by ultrafine particles (<0.1 μm diameter) due to vehicle exhaust emissions as verified by high correlation with NOx. But PNC contribute only marginally to PM10, due to the small size of exhaust particles. Instead wear of the road surface is an important factor for the highest PM10 concentrations observed. In Stockholm, road wear increases drastically due to the use of studded tires and traction sand on streets during winter; up to 90% of the locally emitted PM10 may be due to road abrasion. PM10 emissions and concentrations, but not PNC, at kerbside are controlled by road moisture. Annual mean urban background PM10 levels are relatively uniformly distributed over the city, due to the importance of long range transport. For PNC local sources often dominate the concentrations resulting in large temporal and spatial gradients in the concentrations. Despite these differences in the origin of PM10 and PNC, the spatial gradients of annual mean concentrations due to local sources are of equal magnitude due to the common source, namely traffic. Thus, people in different areas experiencing a factor of 2 different annual PM10 exposure due to local sources will also experience a factor of 2 different exposure in terms of PNC. This implies that health impact studies based solely on spatial differences in annual exposure to PM10 may not separate differences in health effects due to ultrafine and coarse particles. On the other hand, health effect assessments based on time series exposure analysis of PM10 and PNC, should be able to observe differences in health effects of ultrafine particles versus coarse particles.