燃烧源PM2.5凝结洗涤脱除实验研究

利用蒸汽在燃烧源PM2.5表面凝结,促使PM2.5凝结长大,建立一套燃烧源PM2.5凝结洗涤的实验台;考察了颗粒粒径分布、蒸汽添加量、液气比等对两种燃烧源PM2.5凝结洗涤脱除效果的影响。采用电称低压冲击器 (ELPI)在线测试分析燃煤和燃油PM2.5凝结洗涤前后的数浓度和粒径分布特性,并用SEM和XPS对两种不同燃烧源的颗粒进行了形貌和元素组分分析。结果表明,燃煤和燃油产生的PM2.5形貌和组分具有较大的差别,燃煤PM2.5主要为硅铝矿物质,而燃油PM2.5主要为含炭物质;相同条件下,燃煤PM2.5相变脱除效果优于燃油PM2.5;随着蒸汽添加量的增加,两者的脱除效率均升高;随粒径的增大,脱除效率提高;蒸汽添加量为0.08kg/m3时,粒径为0.4μm的燃煤和燃油细颗粒的脱除效率分别81％和72％;此外,适当增加液气比有利于凝结长大含尘液滴的脱除。     

Size-fractionated sampling and chemical analysis by total-reflection X-ray fluorescence spectrometry of PMx in ambient air and emissions

PM 10 and PM 2.5 (PMx) have been recently introduced as new air quality standards in the EU (Council Directive 1999/30/EC) for particulate matter. Different estimates and measurements showed that the limit values for PM 10 will be exceeded at different locations in Europe, and thus measures will have to be taken to reduce PMx mass concentrations. Source apportionment has to be carried out, demanding comparable methods for ambient air and emission sampling and chemical analysis. Therefore, a special ambient-air sampler and a specially designed emission sampler have been developed. Total-reflection X-ray fluorescence analysis (TXRF) was used for multi-element analyses as a fast method with low detection limits. For ambient air measurements, a sampling unit was built, impacting particle size classes 10–2.5 μm and 2.5–1.0 μm directly onto TXRF sample carriers. An electrostatic precipitator (ESP) was used as back-up filter to also collect particles <1 μm directly onto the TXRF sample carriers. Air quality is affected by natural and anthropogenic sources, and the emissions of particles <10 μm and <2.5 μm, respectively, have to be determined to quantify their contributions to the so-called coarse (10–2.5 μm) and fine (<2.5 μm) particle modes in ambient air. For this, an in-stack particle sampling system was developed, according to the new ambient air quality standards and in view of subsequent analysis by TXRF. These newly developed samplers, in combination with TXRF analyses, were employed in field campaigns to prove the feasibility and capabilities of the approach. Ambient air data show the quantification of a wide spectrum of elements. From those concentrations, PMx ratios were calculated as an indicator for different sources of elements. Results useful for source apportionment are also the elemental day/night ratios calculated to determine local contributions to PMx mass concentrations. With regard to the emission measurements, results of mass and elemental concentrations obtained in two different processes (steel industry) show that the new PM 10/PM 2.5 cascade impactor and measurements with TXRF give characteristic fingerprints for different sources. Size-fractionated ambient air and emission sampling, together with multi-element analysis, prove to be a useful approach to derive information for source–receptor modeling, a method necessary to set up effective abatement strategies to reduce PMx mass concentrations.     

Speciation of copper and zinc in size-fractionated atmospheric particulate matter using total reflection mode X-ray absorption near-edge structure spectrometry

The health effects of aerosol depend on the size distribution and the chemical composition of the particles. Heavy metals of anthropogenic origin are bound to the fine aerosol fraction (PM_2.5). The composition and speciation of aerosol particles can be variable in time, due to the time-dependence of anthropogenic sources as well as meteorological conditions. Synchrotron-radiation total reflection X-ray fluorescence (SR-TXRF) provides very high sensitivity for characterization of atmospheric particulate matter. X-ray absorption near-edge structure (XANES) spectrometry in conjunction with TXRF detection can deliver speciation information on heavy metals in aerosol particles collected directly on the reflector surface. The suitability of TXRF-XANES for copper and zinc speciation in size-fractionated atmospheric particulate matter from a short sampling period is presented. For high size resolution analysis, atmospheric aerosol particles were collected at different urban and rural locations using a 7-stage May cascade impactor having adapted for sampling on Si wafers. The thin stripe geometry formed by the particulate matter deposited on the May-impactor plates is ideally suited to SR-TXRF. Capabilities of the combination of the May-impactor sampling and TXRF-XANES measurements at HASYLAB Beamline L to Cu and Zn speciation in size-fractionated atmospheric particulate matter are demonstrated. Information on Cu and Zn speciation could be performed for elemental concentrations as low as 140 pg/m³. The Cu and Zn speciation in the different size fraction was found to be very distinctive for samples of different origin. Zn and Cu chemical state typical for soils was detected only in the largest particles studied (2–4 μm fraction). The fine particles, however, contained the metals of interest in the sulfate and nitrate forms.     

Study of seasonal variation and source characteristic of PM10 of Shanghai urban atmosphere using PIXE

This study is a one-year monitoring of the inhalable particulate matter (PM10) of Shanghai (from January 2006 to December 2006) to study PM10 pollution. Proton-induced X-ray emission (PIXE) was used to investigate the chemical elements in Shanghai PM10. The study finds seasonal variation in both mass concentration and of chemical elements in PM10. The results of the enrichment factor show that the chemical elements in the inhalable particles could be divided into two categories, soil elements from earth crust and anthropogenic pollution elements. The high enrichment factors suggest that anthropogenic activities were the dominant source for elements such as S, Cu, Cl, Zn, Pb and Br. Strong correlation of K, Ca, Fe and Ti, from factor analysis, indicates these elements coming from earth crust or soil, S, Zn and Pb from industrial pollution and/or traffic and Cl from coal combustion.     

Carbonaceous aerosol in the breathable particulate matter (PM10) in urban area

Carbonaceous material is a large fraction of urban aerosol and it is classified into Elemental Carbon (EC) and Organic Carbon (OC). EC particles are emitted from combustion sources. Because most combustion sources are anthropogenic and generally EC does not undergo chemical transformations, EC is a good indicator of primary anthropogenic primary pollution. OC particles species are emitted from primary emission sources either anthropogenic or biogenic sources. In this paper we have measured the ground concentration of Particulate Matter (PM), Total Carbon (TC), EC and OC in two Monitoring Stations in Rome. The first station is situated downtown Rome (near S.M. Maggiore Cathedral) where the traffic emission flux is strong. The second station is located in the inner a green park (Villa Ada Park): this site is not directly influenced by anthropogenic emissions. The results show that in Rome the TC contribution is about 30% of PM and the OC/EC vary between 0.5 and 1.5 according to the site we are considering. About the chemical particle composition the long-chain carboxylic have been identified as major constituent of organic aerosol and a range values are reported for two important compound class, the Polyciclic Aromatic Hydrocarbons and the nitro-PAHs wich are at very low levels.     

The use of neutron activation analysis for particle size fractionation and chemical characterization of trace elements in urban air particulate matter

The concentration of more than 25 trace elements have been determined in total air particulate matter and in the size segregated fractions from the urban area of Pavia (North Italy). The PM10 fraction was also collected and analyzed. A study of the solubility in water and in physiological solution of the trace elements contained in the PM10 was also carried out. The resulting solutions were further submitted to column chromatography using Chelex 100 to perform a preliminary chemical characterization. INAA was used as the main analytical technique. ET-AAS was used for all Pb and Cd measurements and, in some cases, for the analysis of V, Mn, Cu and Ni.     

Experimental Study on Purification of Diesel Particulate Matter by Non-thermal Plasma Technology

In order to investigate the effects of non-thermal plasma (NTP) on diesel particulate matter (PM), an engine test bench was built up. An engine exhaust particle sizer (EEPS) was introduced to analyze the emission concentration and size distribution of PM and a thermo-gravimetric analyzer was used to analyze the effects of NTP on the composition of the particulate matter in the exhaust gas. The results show that the size distribution interval of the particle mass concentration falls behind that of the quantity concentration under various loads. When the diesel engine operating speed is 2400 rpm and the load is 25%, after NTP, the proportions of the nucleation mode particles and the accumulative mode particles exhibit a small fluctuation while the proportion of ultrafine particles decreases by 10% due to their large quantity concentration. Under the dual effect of DPF and NTP, the particle quantity concentration decreases by 98%. In order to investigate the effect of NTP on the composition of the PM, a thermo-gravimetric analysis of the particles obtained before and after NTP was carried out. The results show that the proportion of volatile matter falls by 16.05% and solid carbon accounts for an increase of 7.29%. NTP has the ability to improve reduction activity of particles and make particles easier to be oxidized at a lower temperature.     

On-line analysis of ambient air aerosols using laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy is developed for the detection of aerosols in ambient air, including quantitative mass concentration measurements and size/composition measurements of individual aerosol particles. Data are reported for ambient air aerosols containing aluminum, calcium, magnesium and sodium for a 6-week sampling period spanning the Fourth of July holiday period. Measured mass concentrations for these four elements ranged from 1.7 parts per trillion (by mass) to 1.7 parts per billion. Ambient air concentrations of magnesium and aluminum revealed significant increases during the holiday period, which are concluded to arise from the discharge of fireworks in the lower atmosphere. Real-time conditional data analysis yielded increases in analyte spectral intensity approaching 3 orders of magnitude. Analysis of single particles yielded composition-based aerosol size distributions, with measured aerosol diameters ranging from 100 nm to 2 μm. The absolute mass detection limits for single particle analysis exceeded sub-femtogram values for calcium-containing particles, and was on the order of 2–3 femtograms for magnesium and sodium-based particles. Overall, LIBS-based analysis of ambient air aerosols is a promising technique for the challenging issues associated with the real-time collection and analysis of ambient air particulate matter data.     

Characterization and Identification of Polycyclic Aromatic Hydrocarbons in Diesel Particulate Matter

Emission of toxic exhaust from diesel engines is one of the major problems associated with the use of petroleum fuels. Particulate matter emission is perceived as a major pollutant, detrimental to the human health and environment, and has led to considerable study. Vehicular emissions comprise toxic pollutants that include unburnt hydrocarbons, polycyclic aromatic hydrocarbons, dioxins, and others. In this study, experiments have been carried out with the objective of determining overall particulate matter chemical composition and size. Electron microscopic images of the emitted soot were studied for average particle size distribution. More than 50 percent of the particles were in the range of 25 to 35 nanometers. Approximately 7, 9, 16, and 5 percent of the measured particles were from 35 to 40, 40 to 45, 45 to 50, and 50 to 55 nanometers, respectively. Determined elements were Al, Ba, Ca, K, Mg, Ti, Zn, and Zr at concentrations of 727, 53, 1100, 701, 1145, 638, 177, and 800 micrograms per milliliter respectively. Fifteen polycyclic aromatic hydrocarbons were detected in the extracts of filters and their concentrations were estimated. This investigation allows the comparison of particulate matter from different fuels and their blends.     

Identification of genotoxic compounds in the airborne particulate matter endowed by small aerodynamic diameter in the city of Catania (Italy)

Airborne particulate matter (PM) is one of the most important polluting factors in the atmosphere containing solid particles generated during the combustion processes. PM, due to the particle size, is easily inhaled and constitutes a potential hazard for the human health. We previously documented, using in vitro cell culture systems, cytogenetic damages caused by exposure to a non-fractionated PM in two different areas from the city of Catania (Sicily, Italy). In the present work, the PM was fractionated in six different sub-fractions, and the relative extractable organic matters (EOM) were analyzed in order to quantify the presence of Polycyclic Aromatic Hydrocarbons (PHAs), a well known class of genotoxic agents. More than 70% of the total EOM was found in the PM with aerodynamic diameters less than 3.5 microm (PM35), and about 60% of the total EOM was detected between PM0.14 and PM1.2. Also the large amount of all the analyzed PAHs were found between the PM0.14 and PM1.2. The obtained data indicates that the genotoxic effect previously shown on mammalian cells (Chinese hamster epithelial liver cells) should be due, in the large part, to the PM with smaller particle size, namely less than PM1.2.     

Iodine speciation in size fractionated atmospheric particles by isotope dilution mass spectrometry

An isotope dilution mass spectrometric method has been developed for the accurate and sensitive determination of iodide and iodate in aerosol particles of the atmosphere. The direct iodine speciation has been possible by the use of species specifically (129)I enriched spike solutions and separation of the isotope diluted species by anion exchange chromatography after water extraction of the filters. Size fractionated collection of aerosol particles by a six stage impactor system shows different distributions of iodide and iodate for particles of different size with specific patterns for anthropogenically influenced continental and unpolluted marine aerosols, respectively. The detection limit for particulate iodide and iodate has been (3-5) pg/m(3) for sampling volumes of 3000 m(3). Oil, used for heating plants, could be identified as one but not the only anthropogenic iodine source.     

Chemical fractionation of elements in airborne particulate matter: primary results on PM10 and PM2.5 samples in the Lazio region (central Italy)

This paper describes how a two-step chemical fractionation method that allows the determination of 17 elements in airborne particulate matter, has been applied to a monitoring campaign of PM10 and PM2.5 in the Lazio region (Italy). This method involved an extraction in a pH buffered aqueous solution followed by a microwave-assisted acid digestion of the residue. With respect to the determination of the total elemental contents, the evaluation of a soluble fraction provides more reliable information on the presence and of the destiny of heavy metals in the environment. Furthermore, the pH buffered extraction conditions chosen, rendered the results independent of the intrinsic acidity of the collected samples and, although the chemical fractionation has a purely operational function, it facilitates the study of the relationship between the distribution of solubility and the different emission sources. Results are discussed in relation to the different concentration and the different degrees of solubility of the elements observed in two sampling sites; one in an urban and one in a rural environment. Since in-parallel sampling of PM2.5 and PM10 were performed in both sites, the influence of particle size is also discussed. Behaviour of some tracers deriving from both vehicular traffic, with particular attention to re-suspended road dusts, and naturally generated particulate matter, such as marine aerosol and Saharian dust, are discussed.     

Concentration levels and temporal variations of heavy elements in the urban particulate matter of Navi Mumbai, India

Coarse and fine fractions of particulate matter (PM) were collected and analysed for trace elements using Instrumental Neutron Activation Analysis and Energy Dispersive X-ray Fluorescence techniques. The result showed high concentrations of Fe, S, Zn and Pb in both the size fractions. The elemental data obtained is used to analyze the temporal and seasonal variations. The trend showed maximum concentrations of PM and metals during winter and minimum during the monsoon season. Enrichment Factor (EF) and source analysis was performed for the same data set to identify the strength of contribution of anthropogenic sources and the possible contributing sources in the study area. EF studies showed high enrichments of Zn, Pb and As in the fine fraction particles. Crustal, vehicular and industrial emissions are identified as the major contributing sources of PM in the study area.     

Mn掺杂Ce0.7Zr0.3O2催化剂同时去除碳烟和氮氧化物的性能

采用柠檬酸络合燃烧法制备了一系列x%Mn/Ce0.7Zr0.3O2(x=0,5,10,15,30,50)复合金属氧化物催化剂,对其同时去除柴油机尾气中碳烟颗粒物(PM)和氮氧化物(NOx)反应的催化活性进行了评价,并采用XRD、低温氮吸附-脱附、H2-TPR、O2-TPD和原位漫反射红外光谱(in situ DRIFTS)等技术对催化剂的性能进行了表征。结果表明,不同含量Mn掺杂入铈锆固溶体中均形成了三元固溶体催化剂,在同时去除PM和NOx的催化反应中,固溶体催化剂的催化活性与其氧化能力直接相关。其中30%Mn/Ce0.7Zr0.3O2催化剂具有较好的同时去除PM和NOx的催化活性,催化去除PM的Ti和Tm分别为298和504℃,NO的转化率达到30.6%。结合O2-TPD和原位红外结果可知,30%Mn/Ce0.7Zr0.3O2表面吸附的超氧物种(O2-)及其与NO反应生成的硝酸盐物种(NO3-)是同时去除PM和NO反应的主要活性物种,进而指出PM和NO在30%Mn/Ce0.7Zr0.3O2表面反应过程中形成了异氰酸盐(-NCO)中间物种,在原位红外实验的基础上提出了30%Mn/Ce0.7Zr0.3O2复合氧化物催化剂同时去除PM和NOx的反应机理。     

Particle Emission from Welding of Painted Steel

The particulate emission caused by welding of steel plates covered with 29 diversified shop primers has been investigated. The investigation includes the determination of particle mass, particle size distribution, and of the contents of heavy metals such as lead and cadmium. The results show that all investigated primers except those with high concentration of zinc pigment produce mass emissions which are very low in comparison to manual arc welding with covered electrode and CO₂-welding on uncoated steel. The emitted particles of the primers are smaller than 1 μm particle diameter and therefore respirable. Lead and cadmium was found in particles emitted during the welding process of all investigated primers. The highest amount was found in particles of primers with high contents of zinc and ferric oxide.     

煤粉物化特性对燃烧后灰颗粒物的影响

以三种煤粉在沉降炉中做燃烧实验,用Andersen粒子撞击器分离并捕集燃烧后的灰颗粒物,借助于压汞仪、扫描电镜及能谱、ICP-AES等对煤粉及分级颗粒物进行检测,研究煤粉物化特性对灰颗粒物的粒径分布、形貌、组成、痕量元素的富集等特性的影响。结果表明,煤粉孔结构、组分的赋存方式及含量等影响其破碎行为及组分迁移、转化的过程...     

Determination of elemental and ionic compositions for diesel exhaust particles by particle induced X-ray emission and ion chromatography analysis.

The purpose of this study is to clarify the chemical characterization of PM2.5 and PM10 in diesel exhaust particles (DEP). Sampling of PM2.5 and PM10 in DEP was carried out in November 1999 using an automobile exhaust testing system at the National Traffic Safety and Environment Laboratory, with a diesel truck (engine type: direct injection, displacement: 7,961 cc, carrying weight: 2,020 kg, equivalent inertia weight: 5,600 kg) placed on a chassis dynamometer. Sampling conditions included idling, constant speed of 40 km/h, M-15 test pattern and 60%-revolution/40%-load of maximum power. Samples were collected on a polycarbonate membrane filter (Nuclepore, pore size: 0.8 microm) using a MiniVol Portable Air Sampler (Airmetrics Co., Inc.). The concentrations of several elemental and ionic species in the PM2.5 and PM10 samples were determined by particle induced X-ray emission (PIXE) and ion chromatography analysis. PIXE analysis of the PM2.5 and PM10 samples revealed 15 elements, of which Na, Mg, Si, S, Cl, Ca, Fe and Zn were found to be the major components. Ionic species were Cl-, NO2-, NO3-, SO4(2-), Na+, NH4+, K+ and Ca2+. Concentrations of elements and ionic species under the sampling condition of 60%-revolution/40%-load were highest in comparison with those of the other sampling conditions. The elemental and ionic species data were compared for PM2.5 and PM10; PM2.5 concentrations were 70% or more of PM10 concentrations for the majority of elements, and concentrations of ionic species in PM2.5 and PM10 were almost identical.     

Study of size-fractionated coal-combustion aerosols using instrumental neutron activation analysis

The chemical composition of aerosols emitted during coal combustion was studied as a function of particle size down to 0.01 m. The aerosol collections were carried out in a 81 MW capacity boiler that burned Venezuelan coal in a circulating fluidized bed combustion chamber. The samples were analyzed with upstream of the electrostatic precipitator using a Berner low-pressure impactor, which was quipped with a cyclone pre-cutter to avoid overloading of the first impaction stages. The samples were analyzed by INAA for up to about 40 elements. The elemental concentrations in the particulate matter for each impaction stage were plotted as a function of stage number (particle size). For the elements Na, Al, K, Ca, Sc, Ti, V, Ga, La and Sm, the concentration variation was limited to a factor of 2 to 4, and the concentrations of these elements were lower for the initial and final impactor stages than for the intermediate particle sizes. The variations were also limited to a factor of 2–4 for Mn, Fe, As, Sb and Th, butall these elements showed increasing concentrations with decreasing particle size. Still other elements, such as Ni, Cr, Co, Za, W, Mo and the halogens, were highly enriched (up to 20–100 fold) in the fine particles when compared with the coarse particles.     

Chemical profile of fugitive particulate emissions

Fugitive emissions pose problems both for general air quality management as well as for the operational management of the facilities. In harbours, activities such loading, unloading and transport of dusty materials are important sources of particulate fugitive emissions. Therefore, there is a growing concern about air quality in these areas as a result of the high impact of the operations on human health and environment. The objectives of this study were to estimate the impact of harbour activities on air particulate matter (APM) levels and to compile an inventory of chemical profiles of harbour particulate fugitive emissions. This preliminary work was based on experimental campaigns carried out in a Portuguese harbour when different types of bulk materials were handled. High time resolution monitors were installed close to the unloaded area and recorded APM concentrations and meteorological variables. PM_2.5 and PM_2.5–10 were collected during unloading operations and a complete chemical characterization of collected samples was made by the techniques k ₀-instrumental neutron activation analysis and particle induced X-ray emission. Results showed that manipulation of materials during harbour operations resulted in high emissions of particles, especially from the coarse fraction. These emissions were very affected by the granulometry and chemical composition of the handled materials and by the meteorological conditions.