Carbonaceous components in atmospheric aerosol: measurement procedures and characterization

Carbonaceous material in the particulate matter was measured in Rome urban area. The carbonaceous material constitutes a significant component of total aerosol mass (30-40%) and it is composed by two main fractions, elemental carbon (EC) and organic carbon (OC). EC is essentially a primary pollutant emitted directly from incomplete combustion processes whereas OC has both primary and secondary origin. A chemical OC investigation has been carried out in order to determine the nalkanes, the n-alkanoic acids, the polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs by means an HRGC-MS procedure. A different seasonal distribution of these compound classes attributed to photochemical radical activity (n-alkanes and PAH decrease in spring- and summertime) and to biogenic plant emission (n-alkanoic acid increase in summertime) has been evidenced.     

Hyphenation of a carbon analyzer to photo-ionization mass spectrometry to unravel the organic composition of particulate matter on a molecular level

The carbonaceous fraction of airborne particulate matter (PM) is of increasing interest due to the adverse health effects they are linked to. Its analytical ascertainment on a molecular level is still challenging. Hence, analysis of carbonaceous fractions is often carried out by determining bulk parameters such as the overall content of organic compounds (OC) and elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC), however, no information about the individual substances or substance classes, of which the single fractions consist can be obtained. In this work, a carbon analyzer and a photo-ionization time-of-flight mass spectrometer (PI-TOF-MS) were hyphenated to investigate individual compounds especially from the OC fractions. The carbon analyzer enables the stepwise heating of particle samples and provides the bulk parameters. With the PI-TOF-MS, it is possible to detect the organic compounds released during the single-temperature steps due to soft ionization and fast detection of the molecular ions. The hyphenation was designed, built up, characterized by standard substances, and applied to several kinds of samples, such as ambient aerosol, gasoline, and diesel emission as well as wood combustion emission samples. The ambient filter sample showed a strong impact of wood combustion markers. This was revealed by comparison to the product pattern of the similar analysis of pure cellulose and lignin and the wood combustion PM. At higher temperatures (450 °C), a shift to smaller molecules occurred due to the thermal decomposition of larger structures of oligomeric or polymeric nature comparable to lignocelluloses and similar oxygenated humic-like substances. Finally, particulate matter from gasoline and diesel containing 10% biodiesel vehicle exhaust has been analyzed. Gasoline-derived PM exhibited large polycyclic aromatic hydrocarbons, whereas diesel PM showed a much higher total organic content. The detected pattern revealed a strong influence of the biodiesel content on the nature of the particulate organic material.     

校园室内外大气PM2.5中的含碳气溶胶及室内源特征

分夏、冬季采集南昌大学前湖校区室外和3个不同室内环境中的PM2.5,测定有机碳(OC)和元素碳(EC),并分析室内、外碳气溶胶质量浓度及其分布特征;利用OC-EC关系式半定量分析室内排放源;结合室内、外二次有机碳(SOC)和SOC/OC的分布进一步讨论不同室内排放源的特征及对SOC的影响;对4个采样点的8个碳组分丰度特征比较分析,结果表明复印/打印机对室内OC的贡献高,8个碳组分的丰度分布特征与其它排放源具有较明显的差异。     

Microstuctural analysis and determination of PM10 emission sources in an industrial Mediterranean city

Scientists are interested in knowing more about the control of sources which contribute to environmental pollution. Air pollution has two main sources: anthropogenic and natural sources. The natural contributions to environmental pollution can be assessed, but cannot be totally controlled. while the emissions from the anthropogenic sources can be controlled. These air pollutants can be dispersed and transferred by winds in the atmosphere. The focus area of this study is the Mediterranean basin. The most important winds in this area are the land and sea breezes. Scanning Electron Microscopy (SEM) was applied to characterize the morphology of the PM10 samples in order to identify possible emission sources for the occuring pollution. Energy Dispersive X-ray Spectroscopy (EDS) was performed for the elemental analysis and chemical characterization of the PM10 samples. The analysis showed that the PM10 samples can be divided into three different groups: the samples containing mineral phases, the compounds from combustion processes and the particles emitted from high-temperature processes.      

Carbonaceous species of TSP in urban and rural sites around coal-fired power stations in northwestern Greece

Total suspended particles from urban and rural locations around an industrial complex with four coal-fired power stations were collected for a period of 6 months (January-June 2001). Mass concentrations of TSP and carbonaceous species (TC, EC, OC and BC) were determined for seven sampling sites of the studied area. The contribution of TC mass to the total particle mass was similar for all sites with an average value of 12.36±1.27%. The fraction of elemental carbon (EC) was estimated between 32 and 46% of the total carbon (TC). The relationship between organic and elemental carbon showed the primary origin of organic carbon (direct emissions). The OC/BC ratio values were also considered in order to get information about the enrichment of aerosols in organic carbon. Four conditional categories out of the sampling site ‘collection were additionally extracted (“urban”, “rural”, “far” and “close” location to the power stations) and considered with respect to the values of the ratios OC/BC and OC/EC and the multiple correlation coefficients R² for the concentrations of OC, BC and EC. It has been found that in some cases the correlation coefficients rather than the ratios could inform on the type of site.     

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.     

基于高分辨质谱在线观测的2011深圳大运会前后PM_1化学组成与粒径分布

本文利用先进的高分辨飞行时间气溶胶质谱仪（HR-ToF-AMS）于2011年深圳世界大学生运动会前后（2011年8月3日~9月22日）对深圳市区大气亚微米细粒子（PM1）化学成分和粒径分布进行了在线测量.结果表明,整个观测期间PM1质量浓度平均为51.1±32.6gm3,其中有机物占颗粒物总质量的37.9%,硫酸盐为37.1%,铵盐11.9%,黑碳6.6%（由一台单颗粒黑碳光度计（SP2）单独测量）,硝酸盐5.8%,氯化物0.6%.观测期间各成分（除黑碳外）的粒径分布峰值位于真空动力学粒径550nm附近,而有机物在较小粒径范围（100~200nm）仍有较多质量分布,显示出本地一次源的明显贡献.基于高分辨有机质谱计算得到的有机气溶胶的平均元素组成为：碳34.0%、氢53.2%、氧12.0%和氮0.8%（原子个数百分比）,对应的OM/OC（有机物与有机碳质量比）平均值为1.66±0.16.采用正矩阵因子解析（PMF）模型对有机气溶胶高分辨质谱进行因子解析,得到三类有机气溶胶：HOA（还原态有机气溶胶）,SV-OOA（半挥发氧化态有机气溶胶）和LV-OOA（低挥发氧化态有机气溶胶）,分别占有机物总量的31.3%,39.8%和28.9%,说明二次有机气溶胶（以SV-OOA和LV-OOA之和代表）是有机气溶胶的主体部分.结合气团来源分析不同时段PM1化学组成和粒径分布特征表明,大运会召开期间PM1质量浓度水平比整个观测期间的平均值低60.7%,是气团来自洋面等有利气象条件和黄标车限行等污染源控制措施的综合作用结果.     

A novel particle sampling system for physico-chemical and toxicological characterization of emissions

Several studies have shown that combustion-derived fine particles cause adverse health effects. Previous toxicological studies on combustion-derived fine particles have rarely involved multiple endpoints and a detailed characterization of chemical composition. In this study, we developed a novel particle sampling system for toxicological and chemical characterization (PSTC), consisting of the Dekati Gravimetric Impactor (DGI) and a porous tube diluter. Physico-chemical and toxicological properties of the particles emitted from various combustion sources were evaluated in two measurement campaigns. First, the DGI was compared with the High-Volume Cascade Impactor (HVCI) and to the Dekati Low-Pressure Impactor (DLPI), using the same dilution system and the same sampling conditions. Only small differences were observed in the mass size distributions, total particulate matter (PM), and particulate matter with diameter smaller than 1 um (PM(1)) concentrations and geometric mass mean diameters (GMMD) between these three impactors. Second, the PSTC was compared with the HVCI sampling system, which has been optimal for collection of particulate samples for toxicological and chemical analyses. Differences were observed in the mass size distributions, total PM and PM(1) emissions, and GMMDs, probably due to the different sampling and dilution methods as well as different sampling substrates which affected the behavior of semi-volatile and volatile organic compounds. However, no significant differences were detected in the in vitro measurements of cytotoxicity between the samples collected with the PSTC and the HVCI systems. In measurements of genotoxicity, significant differences between the two sampling systems were seen only with the particles emitted from the sauna stove. In conclusion, due to compact size, PSTC is an applicable method for use in particle sampling as part of the toxicological and chemical characterization of particulate emissions from different combustion sources. It offers some advantages compared to the previously used high-volume sampling methods including compactness for field measurements, simple preparation of sample substrates and high extraction efficiency.     

广州大气细粒子中有机碳、元素碳和水溶性有机碳的分布特征

在广州市中山大学采样点进行了为期1年的大气细粒子(PM2.5)采样,监测分析得到PM2.5及有机碳(OC)、元素碳(EC)和水溶性有机碳(WSOC)等组分的质量浓度,并进行了比较和评价分析。结果表明广州市细粒子碳污染较严重。对OC、EC和WSOC质量浓度的月变化和季节变化特征进行了讨论,并分析了原因。OC、EC浓度相关性好,表明OC、EC来源大部分相同。根据OC/EC比值,估算二次有机碳(SOC)量,结果是SOC占OC的1/3。讨论了SOC和SOC/OC比值的季节分布,结果证明SOC夏季生成比冬季多。     

Environmetric modeling of emission sources for dry and wet precipitation from an urban area

Monitoring data from chemical analysis of rainwater and aerosol samples collected in an urban area have been interpreted by the use of environmetric approaches. An attempt was done to compare the data set structures of both type of precipitation and to estimate the contribution of different anthropogenic and naturally occurring emission sources to the total mass of the wet and dry precipitation. It was found that three latent factors explaining over 80% of the total variance of the set are responsible for the rainwater set structure-'sea spray', 'soil dust', and 'anthropogenic'. Only two were the latent factors explaining the dominant part of the variance in the case of aerosol samples-'anthropogenic' and 'natural'. It is shown that the anthropogenic influence for aerosol samples is more complex that that of rainwater samples and represents interaction between typical anthropogenic sources and natural emitters. Additionally, a source apportioning using multiple regression on absolute principal component scores is performed in order to obtain qualitative information about the impact of the different identified emission sources on the urban environment.     

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.     

Measurement of the carbonaceous component in the Milan urban particulate matter

The carbonaceous component in the Milan urban particulate matter, i.e. the two components black carbon (BC) and organic carbon (OC), has been measured by means of a thermogravimetric analyzer combined with an infrared spectrophotometer (TGA/FT-IR). While black carbon may be considered a primary pollutant, organic carbon includes both primary emissions and secondary organic aerosols. Since carbonaceous aerosol (including a small quantity of inorganic carbon, too) makes up roughly from 25% to 50% of the average annual PM 2.5 mass concentration, a deeper understanding of this component is required. The TGA/FT-IR technique, employed for the first time to our knowledge for the quantification of the particulate matter carbonaceous component, allows, thought the results here presented are preliminary, to assess the two components BC and OC in a simple way especially if compared with the methods reported in the literature. The total carbon (TC) determinations performed by TGA/FT-IR on Milan urban particulate matter are in good agreement with the results obtained by a total organic carbon (TOC) analyzer operating directly on the solid sample.     

Die Rolle des Aerosols im Klimasystem

Atmospheric aerosol particles cause one of the largest uncertainties in estimates of human influence on climate – a good reason to take a closer look at the atmospheric life cycle of the aerosols and its effects. Besides a number of primary and secondary natural aerosol sources we need to consider since the beginning of industrialisation strong manmade particle sources. During its residence in the atmosphere the aerosol interacts in many physical and chemical ways with other atmospheric trace substances, most importantly with water vapor and its liquid and solid phases. Through its direct effect on solar and thermal radiation and through its influence on clouds the atmospheric aerosol exerts a climate forcing. To data we cannot predict the ensuing climate response because of our limited understanding of essential atmospheric processes and of the many possible feedbacks within the climate system. However, already our present knowledge of the role of the atmospheric aerosol in the climate system makes strictly global views of anthropogenic climate changes questionable.     

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.     

Heavy metal determination in atmospheric particulate matter by Instrumental Neutron Activation Analysis

Instrumental Neutron Activation Analysis (INAA) is employed for its important analytical properties. Fundamentally, INAA is a multi-elemental technique allowing the determination of about 40 elements with a good Limit of Detection. In this paper we applied this nuclear technique to study the element composition in PM10 determining about 30 elements.25 filters were collected in downtown Rome from October 1999 to April 2000 and irradiated at the nuclear reactor Triga Mark II (ENEA-Casaccia Laboratories). The γ-ray measurements have allowed the quali- and quantitative analysis. The element levels in PM10 with the relative correlations have been determined: basically, the concentrations are very low.Furthermore, the enrichment factors of all elements will be reported in order to understand the natural or anthropogenic origins of the particulate matter: some elements may be attributed to long-range transport phenomena from other natural and/or anthropogenic sources.     

Seasonal characteristics of biomass burning contribution to Beijing aerosol

Along with the rapid economic growth and urbani-zation, a number of cities in China are facing the problem of severe air pollution with airborne particles (particulate matter) as the major pollutant identified most frequently. Urban airborne particles are…     

Local and non-local sources of airborne particulate pollution at Beijing--The ratio of Mg/Al as an element tracer for estimating the contributions of mineral aerosols from outside Beijing

A new element tracer technique has firstly been established to estimate the contributions of mineral aerosols from both inside and outside Beijing. The ratio of Mg/Al in aerosol is a feasible element tracer to distinguish between the sources of inside and outside Beijing. Mineral aerosol, inorganic pollution aerosol mainly as sulfate and nitrate, and organic aerosol are the major components of airborne particulates in Beijing, of which mineral aerosol accounted for 32%―67% of total suspended particles (TSP), 10%―70% of fine particles (PM2.5), and as high as 74% and 90% of TSP and PM2.5, respectively, in dust storm. The sources from outside Beijing contributed 62% (38%―86%) of the total mineral aerosols in TSP, 69% (52%―90%) in PM10, and 76% (59%―93%) in PM2.5 in spring, and 69% (52%―83%), 79% (52%―93%), and 45% (7%―79%) in TSP, PM10, and PM2.5, respectively, in winter, while only ～20% in summer and autumn. The sources from outside Beijing contributed as high as 97% during dust storm and were the dominant source of airborne particulates in Beijing. The contributions from outside Beijing in spring and winter are higher than those in summer, indicating clearly that it was related to the various meteorological factors.     

塔克拉玛干沙漠黑碳气溶胶的特性及来源

长期监测并采集塔克拉玛干沙漠腹地的大气颗粒物及黑碳气溶胶样品.在塔克拉玛干沙漠腹地,沙尘气溶胶中的黑碳在PM10中的年平均含量高达1.14%,这说明在人迹罕至的塔克拉玛干沙漠地区,其上空的沙尘气溶胶也已经受到人为活动的影响.黑碳气溶胶具有明显的季节变化和日变化,冬季最高,平均达2261.7ngm-3,依次为冬季春季秋季夏季.黑碳气溶胶日变化特征与城市地区恰好相反,夜间高于白天,午夜0:00～2:00出现峰值,而在上午8:00～11:00出现低值.非沙尘暴期间黑碳对PM10的贡献是沙尘暴时期的11倍.塔里木盆地周边绿洲带人为活动,尤其是新疆南北部地区跨越春秋冬三季的居民采暖所产生的黑碳经由局地、区域或长途传输是塔克拉玛干沙漠腹地黑碳气溶胶的主要来源,也是沙漠黑碳气溶胶具有明显的季节特征和日变化的主要原因.随着沙尘气溶胶的长途传输,沙漠每年大约输出6.3×104吨黑碳气溶胶,这势必会对全球的气候与环境变化产生一定影响.