Transport of atmospheric fine particulate matter: part 2--findings from recent field programs on the intraurban variability in fine particulate matter

Air quality field data, collected as part of the fine particulate matter Supersites Program and other field measurements programs, have been used to assess the degree of intraurban variability for various physical and chemical properties of ambient fine particulate matter. Spatial patterns vary from nearly homogeneous to quite heterogeneous, depending on the city, parameter of interest, and the approach or method used to define spatial variability. Secondary formation, which is often regional in nature, drives fine particulate matter mass and the relevant chemical components toward high intraurban spatial homogeneity. Those particulate matter components that are dominated by primary emissions within the urban area, such as black carbon and several trace elements, tend to exhibit greater spatial heterogeneity. A variety of study designs and data analysis approaches have been used to characterize intraurban variability. High temporal correlation does not imply spatial homogeneity. For example, there can be high temporal correlation but with spatial heterogeneity manifested as smooth spatial gradients, often emanating from areas of high emissions such as the urban core or industrial zones.     

桂林地区大气细颗粒物(PM2.5)工业排放源清单

通过现场勘测以及走访调研的形式,获得桂林地区2011至2013年工业生产情况统计,参照国内外相关文献资料确定排放因子,并通过数据处理得到桂林地区工业排放源清单。结果表明,近三年桂林地区工业污染源年均向大气排放细颗粒物(PM2.5)10 751.01 t,其中以兴安县贡献量最大,达到5 024.92 t;永福县次之,为2 924.31 t。在企业类型中,以火力发电企业、水泥及砖瓦厂对桂林地区大气排放细颗粒物的贡献量较大,分别为2 540.81、6 544.51和555.13 t。同时,桂林地区以煤炭作为主要燃料,其对大气排放细颗粒物的年均贡献量达到2 672.17 t。     

Sources of fine urban particulate matter in Detroit, MI

Data from the speciation trends network (STN) was used to evaluate the amount and temporal patterns of particulate matter originating from local industrial sources and long-range transport at two sites in Detroit, MI: Allen Park, MI, southwest of both Detroit and the areas of heavy industrial activity; Dearborn, MI, located on the south side of Detroit near the most heavily industrialized region. Using positive matrix factorization (PMF) and comparing source contributions at Allen Park to those in Dearborn, contributions made by local industrial sources (power plants, coke refineries, iron smelting, waste incineration), local area sources (automobile and diesel truck) and long range sources of PM(2.5) can be distinguished in greater Detroit. Overall, the mean mass concentration measured at Dearborn was 19% higher than that measured at Allen Park. The mass at Allen Park was apportioned as: secondary sulfate 31%, secondary nitrate 28%, soil 8%, mixed aged sea and road salts 4%, gasoline 15%, diesel 4%, and biomass burning 3%. At Dearborn the mass was apportioned as: secondary sulfate 25%, secondary nitrate 20%, soil 12%, mixed aged sea and road salts 4%, gasoline 20%, diesel 8%, iron and steel, 5%, and mixed industrial 7%. The impact of the iron and steel, soil, and mixed aged sea and road salt was much higher at the Dearborn site than at the Allen Park site, suggesting that close proximity to a local industrial complex has a direct negative impact on local air quality.     

Sources of atmospheric carbonaceous particulate matter in Pittsburgh,Pennsylvania

The organic carbon (OC)/elemental carbon (EC) tracer method is applied to the Pittsburgh, PA, area to estimate the contribution of secondary organic aerosol (SOA) to the monthly average concentration of organic particulate matter (PM) during 1995. An emissions inventory is constructed for the primary emissions of OC and EC in the area of interest. The ratio of primary emissions of OC to those of EC ranges between 2.4 in the winter months and 1.0 in the summer months. A mass balance model and ambient measurements were used to assess the accuracy of the emissions inventory. It is estimated to be accurate to within 50%. The results from this analysis show a strong monthly dependence of the SOA contribution to the total organic PM concentration, varying from near zero during winter months to as much as 50% of the total OC concentration in the summer.     

Spatial and temporal variability in urban fine particulate matter concentrations

Identification of hot spots for urban fine particulate matter (PM(2.5)) concentrations is complicated by the significant contributions from regional atmospheric transport and the dependence of spatial and temporal variability on averaging time. We focus on PM(2.5) patterns in New York City, which includes significant local sources, street canyons, and upwind contributions to concentrations. A literature synthesis demonstrates that long-term (e.g., one-year) average PM(2.5) concentrations at a small number of widely-distributed monitoring sites would not show substantial variability, whereas short-term (e.g., 1-h) average measurements with high spatial density would show significant variability. Statistical analyses of ambient monitoring data as a function of wind speed and direction reinforce the significance of regional transport but show evidence of local contributions. We conclude that current monitor siting may not adequately capture PM(2.5) variability in an urban area, especially in a mega-city, reinforcing the necessity of dispersion modeling and methods for analyzing high-resolution monitoring observations.     

Source contributions to fine particulate matter in an urban atmosphere

This paper proposes a practical method for estimating source attribution by using a three-step methodology. The main objective of this study is to explore the use of the three-step methodology for quantifying the source impacts of 24-h PM2.5 particles at an urban site in Seoul, Korea. 12-h PM2.5 samples were collected and analyzed for their elemental composition by ICP-AES/ICP-MS/AAS to generate the source composition profiles. In order to assess the daily average PM2.5 source impacts, 24-h PM2.5 and polycyclic aromatic hydrocarbons (PAH) ambient samples were simultaneously collected at the same site. The PM2.5 particle samples were then analyzed for trace elements. Ionic and carbonaceous species concentrations were measured by ICP-AES/ICP-MS/AAS, IC, and a selective thermal MnO2 oxidation method. The 12-h PM2.5 chemical data was used to estimate possible source signatures using the principal component analysis (PCA) and the absolute principal component scores method followed by the multiple linear regression analysis. The 24-h PM2.5 source categories were extracted with a combination of PM2.5 and some PAH chemical data using the PCA, and their quantitative source contributions were estimated by chemical mass balance (CMB) receptor model using the estimated source profiles and those in the literature. The results of PM2.5 source apportionment using the 12-h derived source composition profiles show that the CMB performance indices; chi2, R2, and percent of mass accounted for are 2.3%, 0.97%, and 100.7%, which are within the target range specified. According to the average PM2.5 source contribution estimate results, motor vehicle exhaust was the major contributor at the sampling site, contributing 26% on average of measured PM2.5 mass (41.8 microg m-3), followed by secondary sulfate (23%) and nitrate (16%), refuse incineration (15%), soil dust (13%), field burning (4%), oil combustion (2.7%), and marine aerosol (1.3%). It can be concluded that quantitative source attribution to PM2.5 in an urban area where source profiles have not been developed can be estimated using the proposed three-step methodology approach.     

Characterization of visibility impacts related to fine particulate matter in Canada

Canada has recently established standards for the management of particulate matter (PM) air quality. National networks currently measure PM mass concentrations and chemical speciation. Methods used in the U.S. IMPROVE network are applied to the 1994--2000 Canadian fine PM data to obtain a regional reconstruction of the visibility based on particle composition. Nationally, the greatest light extinction occurs in the Windsor-Quebec City corridor. Variations in the dominant chemical species responsible for the reduction in visibility are presented for regions across the country. In most regions, sulfate and nitrate contribute most greatly to reduced visibility. The visibility implications of achieving the Canada-Wide Standard (CWS) across the country are evaluated, with the greatest improvement in visibility associated with achieving the CWS in southern Ontario. Elsewhere in the country, achieving the CWS will actually result in deteriorating air quality. Improving current estimates of visibility requires higher spatially and temporally resolved measurements of organic and elemental carbon fractions and particulate nitrate.     

Source apportionment of airborne fine particulate matter in an underground mine

The chemical mass balance source apportionment technique was applied to an underground gold mine to assess the contribution of diesel exhaust, rock dust, oil mists, and cigarette smoke to airborne fine (<2.5 microm) particulate matter (PM). Apportionments were conducted in two locations in the mine, one near the mining operations and one near the exit of the mine where the ventilated mine air was exhausted. Results showed that diesel exhaust contributed 78-98% of the fine particulate mass and greater than 90% of the fine particle carbon, with rock dust making up the remainder. Oil mists and cigarette smoke contributions were below detection limits for this study. The diesel exhaust fraction of the total fine PM was higher than the recently implemented mine air quality standards based on total carbon at both sample locations in the mine.     

Source apportionment of fine particulate matter in the southeastern United States

Particulate matter (PM) less than 2.5 microm in size (PM2.5) source apportionment by chemical mass balance receptor modeling was performed to enhance regional characterization of source impacts in the southeastern United States. Secondary particles, such as NH4HSO4, (NH4)2SO4, NH4NO3, and secondary organic carbon (OC) (SOC), formed by atmospheric photochemical reactions, contribute the majority (>50%) of ambient PM2.5 with strong seasonality. Source apportionment results indicate that motor vehicle and biomass burning are the two main primary sources in the southeast, showing relatively more motor vehicle source impacts rather than biomass burning source impacts in populated urban areas and vice versa in less urbanized areas. Spatial distributions of primary source impacts show that each primary source has distinctively different spatial source impacts. Results also find impacts from shipping activities along the coast. Spatiotemporal correlations indicate that secondary particles are more regionally distributed, as are biomass burning and dust, whereas impacts of other primary sources are more local.     

Molecular composition of organic fine particulate matter in Houston,TX

Organic fine particulate matter collected in Houston, TX between March 1997 and March 1998 was analyzed to determine the concentration of individual organic compounds. Samples from four sites were analyzed including two industrial locations (Houston Regional Monitoring Corporation (HRM-3) site in Channelview and Clinton Drive site near the Ship Channel Turning Basin), one suburban location (Bingle Drive site in Northwest Houston) and one background site (Galveston Island). At the three urban locations, samples were divided into three seasonal sample aggregates (spring, summer and winter), while at the background site a single annual average sample pool was used. Between 10 and 16 individual samples were pooled to get aggregate samples with enough organic carbon mass for analysis. Overall, 82 individual organic compounds were quantified. These include molecular markers which are compounds unique to specific fine particle sources and can be used to track the relative contribution of source emissions to ambient fine particle levels. The differences both spatially and temporally in these tracers can be used to evaluate the variability in emission source strengths.     

Determination of 2-nitrofluoranthene and 2-nitropyrene in ambient particulate organic matter: Evidence for atmospheric reactions

We have identified and quantified 2-nitrofluoranthene (2-NO₂-FL) and 2-nitropyrene (2-NO₂-PY), both strong, direct mutagens in paniculate organic matter (POM) samples collected in polluted ambient air in southern California. Samples were collected during four consecutive 6-h periods on 18–19 September 1984, during which the ambient concentrations of gaseous co-pollutants were characterized by long pathlength spectroscopic techniques and conventional analyzers. Concentrations ranged up to 0.3 ng m⁻³ for 2-NO₂-FL and 0.02 ng m⁻³ for 2-NO₂-PY. The 2-nitro isomers of fluoranthene and pyrene have not been observed in direct emissions of POM (e.g. diesel exhaust and wood smoke). However, we recently observed these isomers from laboratory reactions involving N₂O₅ or OH radicals and the parent compounds. Thus the identification of 2-NO₂-FL and 2-NO₂-PY in ambient POM suggests that chemical transformations of fluoranthene and pyrene may take place in polluted atmospheres.     

Characterization of major chemical components of fine particulate matter in North Carolina

This paper presents measurements of daily sampling of fine particulate matter (PM2.5) and its major chemical components at three urban and one rural locations in North Carolina during 2002. At both urban and rural sites, the major insoluble component of PM2.5 is organic matter, and the major soluble components are sulfate (SO4(2-)), ammonium (NH4(+)), and nitrate (NO3(-)). NH4(+) is neutralized mainly by SO4(2-) rather than by NO3(-), except in winter when SO4(2-) concentration is relatively low, whereas NO3(-) concentration is high. The equivalent ratio of NH4(+) to the sum of SO4(2-) and NO3(-) is < 1, suggesting that SO4(2-) and NO3(-) are not completely neutralized by NH4(+). At both rural and urban sites, SO4(2-) concentration displays a maximum in summer and a minimum in winter, whereas NO3(-) displays an opposite seasonal trend. Mass ratio of NO3(-) to SO4(2-) is consistently < 1 at all sites, suggesting that stationary source emissions may play an important role in PM2.5 formation in those areas. Organic carbon and elemental carbon are well correlated at three urban sites although they are poorly correlated at the agriculture site. Other than the daily samples, hourly samples were measured at one urban site. PM2.5 mass concentrations display a peak in early morning, and a second peak in late afternoon. Back trajectory analysis shows that air masses with lower PM2.5 mass content mainly originate from the marine environment or from a continental environment but with a strong subsidence from the upper troposphere. Air masses with high PM2.5 mass concentrations are largely from continental sources. Our study of fine particulate matter and its chemical composition in North Carolina provides crucial information that may be used to determine the efficacy of the new National Ambient Air Quality Standard (NAAQS) for PM fine. Moreover, the gas-to-particle conversion processes provide improved prediction of long-range transport of pollutants and air quality.     

人体室内外PM_(2.5)吸入暴露研究

介绍了室内外空气颗粒物吸入暴露的评价方法,选择PM2.5作为检测评价的对象,初步评价了上海市某区不同年龄段人员的PM2.5暴露水平。结果表明:(1)成人和老人的全年日平均PM2.5吸入暴露量均较高,并且成人的全年日平均PM2.5吸入暴露量变化曲线和儿童相似。(2)老人室内PM2.5吸入暴露量要明显高于室外,其主要原因是老人在室内时间较长。儿童和成人的室外PM2.5吸入暴露量高于室内。(3)不同人员的年平均PM2.5吸入暴露量的排序为成人老人儿童,其年平均PM2.5吸入暴露量分别为1.141、1.046、0.935mg。     

Emission factors of particulate matter,polycyclic aromatic hydrocarbons,and levoglucosan from wood combustion in south-central Chile

In south-central Chile, wood stoves have been identified as an important source of air pollution in populated areas. Eucalyptus (Eucalyptus globulus), Chilean oak (Nothofagus oblique), and mimosa (Acacia dealbata) were burned in a single-chamber slow-combustion wood stove at a controlled testing facility located at the University of Concepción, Chile. In each experiment, 2.7–3.1 kg of firewood were combusted while continuously monitoring temperature, exhaust gases, burn rate, and collecting particulate matter samples in Teflon filters under isokinetic conditions for polycyclic aromatic hydrocarbon and levoglucosan analyses. Mean particulate matter emission factors were 2.03, 4.06, and 3.84 g/kg dry wood for eucalyptus, oak, and mimosa, respectively. The emission factors were inversely correlated with combustion efficiency. The mean emission factors of the sums of 12 polycyclic aromatic hydrocarbons in particle phases were 1472.5, 2134.0, and 747.5 μg/kg for eucalyptus, oak, and mimosa, respectively. Fluoranthene, pyrene, benzo[a]anthracene, and chrysene were present in the particle phase in higher proportions compared with other polycyclic aromatic hydrocarbons that were analyzed. Mean levoglucosan emission factors were 854.9, 202.3, and 328.0 mg/kg for eucalyptus, oak, and mimosa, respectively. Since the emissions of particulate matter and other pollutants were inversely correlated with combustion efficiency, implementing more efficient technologies would help to reduce air pollutant emissions from wood combustion.

Implications: Residential wood burning has been identified as a significant source of air pollution in populated areas. Local wood species are combusted for home cooking and heating, which releases several toxic air pollutants, including particulate matter, carbon monoxide, and polycyclic aromatic hydrocarbons. Air pollutant emissions depend on the type of wood and the technology and operational conditions of the wood stove. A better understanding of emissions from local wood species and wood stove performance would help to identify better biomass fuels and wood stove technologies in order to reduce air pollution from residential wood burning.     

成都市降水对大气颗粒物湿清除作用的观测研究

为研究成都市降水对大气颗粒物(以下简称颗粒物)的湿清除作用,对2014—2016年成都市的颗粒物(PM_2.5、PM₁₀)和气象观测数据进行分析。结果表明:月、季尺度下,降水对PM_2.5、PM₁₀均有削减作用。降水时段的PM_2.5、PM₁₀浓度较非降水时段分别降低17.1%和15.8%,且冬季降幅最为明显。考察472次降水过程对颗粒物的湿清除作用,发现单次降水过程后PM_2.5、PM₁₀浓度增长频次(243、234次)和削减频次(229、238次)接近,但颗粒物浓度总体呈削减趋势。对于单次降水过程,颗粒物的初始浓度与降水对颗粒物的湿清除作用关系密切,特别是降水持续时间超过8h后,颗粒物初始浓度越高,削减效果越好。     

Large PAHs detected in fine particulate matter emitted from light-duty gasoline vehicles

Emission factors of large PAHs with 6–8 aromatic rings with molecular weights (MW) of 300–374 were measured from 16 light-duty gasoline-powered vehicles (LDGV) and one heavy-duty diesel-powered vehicle (HDDV) operated under realistic driving conditions. LDGVs emitted PAH isomers of MW 302, 326, 350, and 374, while the HDDV did not emit these compounds. This suggests that large PAHs may be useful tracers for the source apportionment of gasoline-powered motor vehicle exhaust in the atmosphere. Emission rates of MW 302, 326, and 350 isomers from LDGVs equipped with three-way catalysts (TWCs) ranged from 2 to 10 (μg L⁻¹ fuel burned), while emissions from LDGVs classified as low emission vehicles (LEVs) were almost a factor of 10 lower. MW 374 PAH isomers were not quantified due to the lack of a quantification-grade standard. The reduced emissions associated with the LEVs are likely attributable to improved vapor recovery during the “cold-start” phase of the Federal Test Procedure (FTP) driving cycle before the catalyst reaches operating temperature. Approximately 2 (μg g⁻¹ PM) of MW 326 and 350 PAH isomer groups were found in the National Institute of Standards and Technology standard reference material (SRM)#1649 (Urban Dust). The pattern of the MW 302, 326, and 350 isomers detected in SRM#1649 qualitatively matched the ratio of these compounds detected in the exhaust of TWC LDGVs suggesting that each gram of Urban Dust SRM contained 5–10 mg of PM originally emitted from gasoline-powered motor vehicles.Large PAHs made up 24% of the total LEV PAH emissions and 39% of the TWC PAH emissions released from gasoline-powered motor vehicles. Recent studies have shown certain large PAH isomers have greater toxicity than benzo[a]pyrene. Even though the specific toxicity measurements on PAHs with MW >302 have yet to be performed, the detection of significant amounts of MW 326 and 350 PAHs in motor vehicle exhaust in the current study suggests that these compounds may pose a significant public health risk.     

Modeled and observed fine particulate matter reductions from state attainment demonstrations

States rely upon photochemical models to predict the impacts of air quality attainment strategies, but the performance of those predictions is rarely evaluated retrospectively. State implementation plans (SIPs) developed to attain the 1997 U.S. standard for fine particulate matter (PM_2.5; denoting particles smaller than 2.5 microns in diameter) by 2009 provide the first opportunity to assess modeled predictions of PM_2.5 reductions at the state level. The SIPs were the first to rely upon a speciated modeled attainment test methodology recommended by the U.S. Environmental Protection Agency to predict PM_2.5 concentrations and attainment status. Of the 23 eastern U.S. regions considered here, all but one achieved the 15 μg/m³ standard by 2009, and the other achieved it the following year, with downward trends sustained in subsequent years. The attainment tests predicted 2009 PM_2.5 design values at individual monitors with a mean bias of 0.38 μg/m³ and mean error of 0.68 μg/m³, and were 95% accurate in predicting whether a monitor would achieve the standard. All of the errors were false alarms, in which the monitor observed attainment after a modeled prediction of an exceedance; in these cases, the states used weight-of-evidence determinations to argue that attainment was likely. Overall, PM_2.5 concentrations at monitors in the SIP regions declined by 2.6 μg/m³ from 2000–2004 to 2007–2009, compared with 1.6 μg/m³ in eastern U.S. regions originally designated as attainment. Air quality improvements tended to be largest at monitors that were initially the most polluted.

ImplicationsAs states prepare to develop plans for attaining a more stringent standard for fine particulate matter, this retrospective analysis documents substantial and sustained air quality improvements achieved under the previous standard. Significantly larger air quality improvements in regions initially designated nonattainment of the 1997 standard indicate that this status prompted heightened control efforts. The speciated modeled attainment test is found to be accurate and slightly conservative in predicting particulate concentrations for the cases considered here, providing confidence for its use in upcoming attainment plans.