Considerations for design of source apportionment studies

This report recommends procedures for source and ambient sampling and analysis in source apportionment studies. The recommendations are based on the results of receptor model studies of atmospheric particles in urban areas, especially a recent study of Houston, TX, undertaken as part of the Mathematical and Empirical Receptor Models Workshop (Quail Roost II). The recommendations are presented at three levels of increasing cost and detail of information obtained. Existing mass emissions inventories combined with chemically resolved test data from similar sources (not necessarily in the same locale) can be used to initially estimate the sources of elements present on ambient particles. To aid local users in construction of chemically resolved emission estimates, the U.S. Environmental Protection Agency (EPA) is compiling a library of compositions and size distributions of particulate emissions from major source types. More reliable source characterization can be achieved if the actual sources are tested directly. EPA should develop and publish detailed procedures for source sampling that would be more appropriate for receptor model use than are existing standard methods. Source and ambient sampling should be conducted by similar methods. If possible, particles from sources should be collected in a way that simulates changes that would normally occur before they reach distant receptors (e.g. by diluting and cooling the particles from hot sources). It is recommended that particulate samples be routinely collected in two size fractions by use of virtual impactors and that all samples be subjected, at a minimum, to mass and X-ray fluorescence analyses. Additional measurements are suggested for obtaining more detailed information: neutron activation analysis; X-ray diffraction; automated particle classification by electron microscopy; analyses for classes of organic species, ¹⁴C and thermally released carbonaceous species; and real-time observation of several gases during sample collection. Methods for collecting meteorological data in parallel with ambient samples are described, as are methods for incorporating such data into the source identification process.     

Receptor modeling application framework for particle source apportionment

Receptor models infer contributions from particulate matter (PM) source types using multivariate measurements of particle chemical and physical properties. Receptor models complement source models that estimate concentrations from emissions inventories and transport meteorology. Enrichment factor, chemical mass balance, multiple linear regression, eigenvector. edge detection, neural network, aerosol evolution, and aerosol equilibrium models have all been used to solve particulate air quality problems, and more than 500 citations of their theory and application document these uses. While elements, ions, and carbons were often used to apportion TSP, PM10, and PM2.5 among many source types, many of these components have been reduced in source emissions such that more complex measurements of carbon fractions, specific organic compounds, single particle characteristics, and isotopic abundances now need to be measured in source and receptor samples. Compliance monitoring networks are not usually designed to obtain data for the observables, locations, and time periods that allow receptor models to be applied. Measurements from existing networks can be used to form conceptual models that allow the needed monitoring network to be optimized. The framework for using receptor models to solve air quality problems consists of: (1) formulating a conceptual model; (2) identifying potential sources; (3) characterizing source emissions; (4) obtaining and analyzing ambient PM samples for major components and source markers; (5) confirming source types with multivariate receptor models; (6) quantifying source contributions with the chemical mass balance; (7) estimating profile changes and the limiting precursor gases for secondary aerosols; and (8) reconciling receptor modeling results with source models, emissions inventories, and receptor data analyses.     

Review of receptor modeling methods for source apportionment

Efforts have been made to relate measured concentrations of airborne constituents to their origins for more than 50 years. During this time interval, there have been developments in the measurement technology to gather highly time-resolved, detailed chemical compositional data. Similarly, the improvements in computers have permitted a parallel development of data analysis tools that permit the extraction of information from these data. There is now a substantial capability to provide useful insights into the sources of pollutants and their atmospheric processing that can help inform air quality management options. Efforts have been made to combine receptor and chemical transport models to provide improved apportionments. Tools are available to utilize limited numbers of known profiles with the ambient data to obtain more accurate apportionments for targeted sources. In addition, tools are in place to allow more advanced models to be fitted to the data based on conceptual models of the nature of the sources and the sampling/analytical approach. Each of the approaches has its strengths and weaknesses. However, the field as a whole suffers from a lack of measurements of source emission compositions. There has not been an active effort to develop source profiles for stationary sources for a long time, and with many significant sources built in developing countries, the lack of local profiles is a serious problem in effective source apportionment. The field is now relatively mature in terms of its methods and its ability to adapt to new measurement technologies, so that we can be assured of a high likelihood of extracting the maximal information from the collected data.

Implications: Efforts have been made over the past 50 years to use air quality data to estimate the influence of air pollution sources. These methods are now relatively mature and many are readily accessible through publically available software. This review examines the development of receptor models and the current state of the art in extracting source identification and apportionments from ambient air quality data.     

Source apportionment with site specific source profiles

A receptor modeling study was performed to identify and apportion the sources of PM10 mass in Granite City, Illinois, an area of historic TSP nonattainment. Samples of the ambient aerosol were collected using a dichotomous sampler. Each sample was analyzed by x-ray fluorescence and instrumental neutron activation analysis. To begin the study, a factor analysis was performed. Two different chemical mass balance (CMB) analyses were then made. The first CMB analysis used only source profiles available from the literature while the second included twelve source profiles developed from dust samples collected in Granite City. Both CMB analyses used 20 of the 33 analyzed elements since many of the source profiles in the literature did not include the other thirteen elements. The results from both sets of CMB analyses were grouped by the predominate wind direction at the site during the time each sample was taken to identify the direction of each source relative to the sampler. It was found that regional sources were the primary contributors to the fine fraction while the coarse fraction was composed of material from local industries. These sources were generally the ones identified during the Regional Air Pollution Study previously conducted in the area. However, the emission profiles from these sources were observed to have changed between the studies. It was also found that the use of the locally generated profiles greatly improved the results of the CMB analysis.     

"二重源解析"技术及其系统实现

化学质量平衡是被广泛用于空气质量管理的受体模型之一.由于混合源(城市扬尘)和单一源因颗粒物源谱的严重共线性,采用美国环境保护署推荐使用的EPA-CMB8.2,无法定量解析出各排放源初始态和扬尘态颗粒物的贡献值和分担率.针对这一问题,完善和规范了"二重源解析"技术原理,开发了具有"二重源解析"功能的NKCMB3.0.对鞍山市样品污染物来源解析的试验结果表明,"二重源解析"技术在对混合源和单一源同时进行源解析时是有效的.     

Interlaboratory comparison of source apportionment procedures: Results for simulated data sets

Three sets of simulated aerosol compositional data were prepared to (1) assess the current state of the art of source apportionment procedures and (2) provide initial sets of test data to aid method development. The data sets were generated from reported source profiles, real meteorological data (St. Louis, 1976) and two constructed city plans. Following plume dispersion by means of the RAM model, 40 ‘samples’ having known source contributions and error structure were generated for each set. Seven laboratories participating in the Mathematical and Empirical Receptor Models Workshop (Quail Roost II) undertook deconvolution of one or two of the sets by various numerical techniques (chemical mass balance or multivariate). Comparison of the participants' results with the known source contributions showed that the source contribution estimates were consistent with the truth within a factor of ~ 2 and that the uncertainty estimates ranged from much too conservative (broad) to much too small. No unique method of choice emerged from this exercise; the participants' various techniques appeared complementary and capable of resolving ~ 6–9 different sources. The intercomparison did allow us to formulate suggestions for improving the simulation process per se and for improving the various treatments (especially with respect to estimating uncertainties).     

水环境多环芳烃源解析研究进展

城市化和工业化给环境带来的潜在危害引起人们对环境质量的重视。污染物来源解析研究的成果为环境管理提供了有效的工具。在查阅大量文献的基础上,综述了应用于水环境尤其是沉积物中多环芳烃源解析的主要理论方法和应用模型,并初步提出了沉积物中多环芳烃源解析方法。     

水环境多环芳烃源解析研究进展

城市化和工业化给环境带来的潜在危害引起人们对环境质量的重视.污染物来源解析研究的成果为环境管理提供了有效的工具.在查阋大量文献的基础上,综述了应用于水环境尤其是沉积物中多环芳烃源解析的主要理论方法和应用模型,并初步提出了沉积物中多环芳烃源解析方法.     

Determination of buffering capacity of total suspended particle and its source apportionment using the chemical mass balance approach

The samples of total suspended particle (TSP) from sources and TSP in the ambient atmosphere were collected in 2006 at Tianjin, People's Republic of China and analyzed for 16 chemical elements, two water-soluble ions, total carbon, and organic carbon. On the basis of the chemical mass balance (CMB) model, the contributions of different TSP sources to the ambient TSP were identified. The results showed that resuspended dust has the biggest contributions to the concentration of ambient TSP. The buffering capacity of each TSP source was also determined by an analytical chemistry method, and the result showed that the constructive dust (the dust emitted from construction work) had the strongest buffering capacity among the measured sources, whereas the coal combustion dust had the weakest buffering capacity. A calculation formula of the source of buffering capacity of ambient TSP was developed based on the result of TSP source apportionment and the identification of the buffering capacity of each TSP source in this study. The results of the source apportionment of the buffering capacity of ambient TSP indicated that open sources (including soil dust, resuspended dust, and constructive dust) were the dominant sources of the buffering capacity of the ambient TSP. Acid rain pollution in cities in Northern China might become serious with a decrease of open source pollution without reducing acidic sources. More efforts must be made to evaluate this potential risk, and countermeasures should be proposed as early as possible.     

Fine particulate source apportionment using data from the USEPA speciation trends network in Chicago,Illinois: Comparison of two source apportionment models

Data from two of the United States Environmental Protection Agency's speciation trends network fine particulate matter sites within Chicago, Illinois were analyzed using the chemical mass balance (CMB) and positive matrix factorization (PMF) models to determine source contributions to the ambient fine particulate concentrations. The results from the two models were compared to determine the similarities and differences in the source contributions. This included examining the differences in the magnitude of the individual source contributions as well as the correlation between the contribution values from the two methods. The results showed that both models predicted sulfates, nitrates and motor vehicles as the three highest fine particle contributors for the two sites accounting for approximately 80% of the total. The PMF model attributed a slightly greater amount of fine particulate to the road salt, steel and soil sources while vegetative burning contributed more in the CMB results. Correlations between the contribution results from the two models were high for sulfates, nitrates and road salt with very good correlations existing for motor vehicles and petroleum refineries. The predicted PMF profiles agreed well with measured source profiles for the major species associated with each source.     

Designing ambient particulate matter monitoring program for source apportionment study by receptor modeling

Particulate matter (PM) receptor modeling requires specific intensive input data that is always a challenge to produce cost effectively. A well-designed monitoring program is important to collect such PM ambient data in urban areas with diverse and densely distributed sources. This paper presents a general framework for designing such a monitoring program while emphasizing appropriate quality assurance and quality control elements that are particularly applicable where limited resources are available. Topics for discussion include selection of monitoring sites, sampling and analytical techniques, and the uncertainty estimation for ambient concentration input data. The design framework is illustrated by a case study of a monitoring program for PM source apportionment in the Bangkok Metropolitan Region in which 24-h fine and coarse PM samples were collected using two collocated dichotomous samplers. Comparison between black carbon measurements by Smoke Stain reflectometry and Thermal Optical Transmittance method is highlighted.     

珠三角秋季臭氧污染来源解析

秋季是珠三角臭氧污染最严重的季节,选取2004年秋季珠三角典型臭氧污染过程,运用臭氧来源解析技术等分析手段,研究珠三角臭氧污染特性,分析并量化各排放源区各类源对受体点的臭氧贡献。结果表明,东莞市对珠江口地区的臭氧峰值有重大贡献,下午2-3点东莞市前体物的臭氧贡献最大可达40ppb;而广州市区的前体物排放主要影响顺德区和南海区。在珠三角,排放源区一般对下风向40km范围内的地区臭氧贡献最大。秋季大多数情况下珠三角西部(江门东湖)臭氧受中部主要排放源区臭氧前体物排放与输送的影响很大,广州和佛山地区对江门东湖的臭氧峰值贡献达50ppb左右。交通尾气排放对珠三角各受体点的臭氧贡献最大,交通源对重污染区受体点臭氧的贡献最高可达40ppb~50ppb。     

大气颗粒物源解析技术研究进展

大气颗粒物源解析技术在环境管理中发挥着越来越重要的作用。本文从受体模型、样品的处理技术、源解析技术发展的最新趋势三方面介绍了大气颗粒物源解析技术的研究进展。     

Organic aerosol source apportionment from highly time-resolved molecular composition measurements

Organic molecular composition measurements with 3.5 min time resolution were performed with the photoionization aerosol mass spectrometer (PIAMS) over an 18-day period in October–November 2007 in Wilmington, Delaware, USA. Mass spectra were obtained for a total of 6244 time periods, and the signal intensities of 60 specific m/z ratios corresponding to key organic molecular species were modeled by positive matrix factorization (PMF). Six factors were identified that could be tentatively linked to specific sources (diesel exhaust, car emissions/road dust, meat cooking) or types of compounds (alkanes/alkanoic acids, phthalates, PAHs). Owing to the inherent high time resolution of PIAMS, the temporal (diurnal) and wind direction dependencies of these factors could be examined in detail to assess the impacts of point sources and atmospheric processes. Time-resolved EC/OC and gas-phase data (O₃, NO_x, CO) were also obtained during the measurement period to help distinguish primary (POC) and secondary (SOC) organic carbon. The total organic carbon (TOC) concentration averaged 2.6 μg m^?3 during the measurement period and most (>90%) was classified as primary. Of this, approximately one-third could be assigned as combustion POC and the other two-thirds as non-combustion POC. The PMF results were combined with EC/OC data for source apportionment. The diesel and car/road dust factors together represented about two-thirds of TOC, while the alkane/alkanoic acid and meat cooking factors contributed most of the remaining one-third. The phthalate and PAH factors contributed very little, only a few percent of the total. The diesel factor correlated most strongly to combustion POC, while the sum of the remaining factors correlated well with non-combustion POC.     

Chemical and physical analyses of Houston aerosol for interlaboratory comparison of source apportionment procedures

Eighteen consecutive 12-h ambient aerosol samples were obtained in Houston, TX, as part of a U.S. Environmental Protection Agency visibility study in that city. The samples were collected on Teflon, Nuclepore and quartz filters by means of dichotomous samplers and were analyzed for mass, elemental and ionic species concentrations by β-ray attenuation. X-ray fluorescence, ion chromatography, colorimetry, instrumental neutron activation analysis and pyrolysis. The specimens and analytical data were distributed to participants of the Mathematical and Empirical Receptor Models Workshop (Quail Roost II), to provide a basis for comparison of source apportionment procedures. Certain workshop participants undertook further analyses of the specimens by X-ray powder diffraction, scanning electron microscopy with automated image analysis and X-ray energy spectroscopy and analytical light microscopy. This report describes all of these analytical procedures. Also, through prototype comparison mechanisms, the elemental, compound and individual particle data are reduced to a common basis (elemental composition), permitting intercomparisons of results from different methods. In general, the intercomparisons suggest that each analytical technique has certain advantages and limitations for receptor modeling and that the various techniques are best viewed as complimentary. Combinations of analytical approaches can lead to improved source resolution in the apportionment calculations.     

Spatial gradients and source apportionment of volatile organic compounds near roadways

Concentrations of 55 volatile organic compounds (VOCs) (C₂–C₁₂) are reported near a highway in Raleigh, NC. Thirty-minute samples were collected at eight locations, ranging from approximately 10–100 m perpendicular from the roadway. The highest concentrations of VOCs were generally measured closest to the roadway, and concentrations decreased exponentially with increasing distance from the roadway. The highest mean concentration for individual VOCs were for ethylene (3.10 ppbv) (mean concentration at x = 13 m), propane (2.27 ppbv), ethane (1.91 ppbv), isopentane (1.54 ppbv), toluene (0.95 ppbv), and n-butane (0.89 ppbv). Concentrations at the nearest roadway location (x = 13 m) were generally between 2.0 and 1.5 times those from the farthest roadway location (x = 92 m). The data were apportioned into four source categories using the EPA Chemical Mass Balance Model (CMB8.2): motor vehicle exhaust, compressed natural gas, propane gas, and evaporative gasoline. The majority of the VOCs resulted from motor vehicle exhaust (67 ± 12%) (% of total VOC at x = 13 m ± S.D.). Compressed natural gas, propane gas, and evaporative gasoline accounted for approximately 15%, 7% and 1% of the total VOC emissions, respectively, at x = 13 m.     

Characteristics and source apportionment of VOCs measured in Shanghai,China

Volatile organic compounds (VOCs) were measured from 2007 to 2010 at the center of Shanghai, China. Because VOCs are important precursors for ozone photochemical formation, detailed information of VOC sources needs to be investigated. The results show that the measured VOC concentrations in Shanghai are dominated by alkanes (43%) and aromatics (30%), following by halo-hydrocarbons (14%) and alkenes (6%). Based on the measured VOC concentrations, a receptor model (PMF; positive matrix factorization) coupled with the information related to VOC sources (the distribution of major industrial complex, meteorological conditions, etc.) is applied to identify the major VOC sources in Shanghai. The result shows that seven major VOC sources are identified by the PMF method, including (1) vehicle related source which contributes to 25% of the measured VOC concentrations, (2) solvent based industrial source to 17%, (3) fuel evaporation to 15%, (4) paint solvent usage to 15%, (5) steel related industrial production to 12%, (6) biomass/biofuel burning to 9%, and (7) coal burning to 7%. Furthermore, ozone formation potential related to VOC sources is calculated by the MIR (maximum incremental reactivity) technique. The most significant VOC source for ozone formation potential is solvent based industrial sources (27%), paint solvent usage (24%), vehicle related emissions (17%), steel related industrial productions (14%), fuel evaporations (9%), coal burning (6%), and biomass/biofuel burning (3%). The weekend effect on the VOC concentrations shows that VOC concentrations are generally higher in the weekdays than in the weekends at the sampling site, suggesting that traffic conditions and human activities have important impacts on the VOC emissions in Shanghai.     

Characterization and source apportionment of wintertime aerosol in a wood-burning community

The continuing upsurge in residential wood combustion has raised questions about potential adverse effects on ambient air quality. A study to investigate the effects of wood-burning emissions on ambient aerosol concentrations was conducted in Waterbury, Vermont, from January to March 1982. Data on total, inhalable and respirable particles (24-h averages) were collected at a central monitoring site and augmented with similar measurements at two auxiliary stations. Mass concentrations were determined gravimetrically and selected samples were analyzed for elemental composition (XRF), polycyclic aromatic hydrocarbons (GC/MS, HPLC), and organic and elemental carbon (thermal-optical method). In addition, continuous data from an integrating nephelometer and a meteorological data acquisition system were collected at the central site. This paper presents results of organic and elemental characterization of wintertime aerosol and examines several different source-apportionment methods, focusing on the contribution of residential wood combustion to measured ambient concentrations.     

Comparison of receptor models for source apportionment of volatile organic compounds in Beijing, China

Identifying the sources of volatile organic compounds (VOCs) is key to reducing ground-level ozone and secondary organic aerosols (SOAs). Several receptor models have been developed to apportion sources, but an intercomparison of these models had not been performed for VOCs in China. In the present study, we compared VOC sources based on chemical mass balance (CMB), UNMIX, and positive matrix factorization (PMF) models. Gasoline-related sources, petrochemical production, and liquefied petroleum gas (LPG) were identified by all three models as the major contributors, with UNMIX and PMF producing quite similar results. The contributions of gasoline-related sources and LPG estimated by the CMB model were higher, and petrochemical emissions were lower than in the UNMIX and PMF results, possibly because the VOC profiles used in the CMB model were for fresh emissions and the profiles extracted from ambient measurements by the two-factor analysis models were "aged".     

Diffuse source apportionment of the Po river eutrophying load to the Adriatic sea: assessment of Lombardy contribution to Po river nutrient load apportionment by means of an integrated modelling approach

The source apportionment of the annual nutrient load carried by the Po river to the Adriatic sea has been studied.

An integrated modelling approach was applied to the Lombardy plain area, which covers about 34% of the Po river watershed area and accounts for about 50% of the point sources’ loads carried by the river. To extract all the information available from direct instream measurements, two different modelling tools were alternatively used. The source apportionment was investigated considering both dry and wet weather scenarios. In order to quantify the apportionment in dry-weather conditions, the Lombardy portion of the Po river basin was modelled by using the US-EPA QUAL2E model. Such a simulation allowed to assess a significant contribution (about 50% of the total dry-weather load) of a not rain-driven diffuse pollution component (i.e. groundwater, springs, lake emissaries). Moreover, to estimate the rain-driven surface runoff contribution to the instream total load, the Lombardy plain area was also modelled by means of the US-DA SWAT model. SWAT results indicate a runoff contribution to the Po river instream total load of about 10 000 t N yr⁻¹ and 1300 t P yr⁻¹ (i.e. approximately the 10–20% of the total annual Lombardy nutrient load). At the event scale (i.e. the single rainstorm event) the runoff contribution may rise up to 30–80% of the total instream load. Finally, the total annual nitrogen load at the Po basin closure was estimated for the period 1985–2001. Out of a total annual load of 140 000 t N yr⁻¹, Lombardy accounts for 43% (point plus diffuse sources). The rain-driven diffuse sources constitute the 20% of the overall total load, the point sources account for 40%, whereas the remaining 40% is mainly constituted by “dry-weather diffuse sources” (i.e. groundwater, springs, lake emissaries).