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1.
Mobile sources are significant contributors to ambient PM2.5, accounting for 50% or more of the total observed levels in some locations. One of the important methods for resolving the mobile source contribution is through chemical mass balance (CMB) receptor modeling. CMB requires chemically speciated source profiles with known uncertainty to ensure accurate source contribution estimates. Mobile source PM profiles are available from various sources and are generally in the form of weight fraction by chemical species. The weight fraction format is commonly used, since it is required for input into the CMB receptor model. This paper examines the similarities and differences in mobile source PM2.5 profiles that contain data for elements, ions, elemental carbon (EC) and organic carbon (OC), and in some cases speciated organics (e.g., polycyclic aromatic hydrocarbons [PAHs]), drawn from four different sources. Notable characteristics of the mass fraction data include variability (relative contributions of elements and ions) among supposedly similar sources and a wide range of average EC:OC ratios (0.60 +/- 0.53 to 1.42 +/- 2.99) for light-duty gasoline vehicles (LDGVs), indicating significant EC emissions from LDGVs in some cases. For diesel vehicles, average EC:OC ratios range from 1.09 +/- 2.66 to 3.54 +/- 3.07. That different populations of the same class of emitters can show considerable variability suggests caution should be exercised when selecting and using profiles in source apportionment studies.  相似文献   

2.
A sensitivity analysis was conducted to characterize sources of uncertainty in results of a molecular marker source apportionment model of ambient particulate matter using mobile source emissions profiles obtained as part of the Gasoline/Diesel PM Split Study. A chemical mass balance (CMB) model was used to determine source contributions to samples of fine particulate matter (PM2.5) collected over 3 weeks at two sites in the Los Angeles area in July 2001. The ambient samples were composited for organic compound analysis by the day of the week to investigate weekly trends in source contributions. The sensitivity analysis specifically examined the impact of the uncertainty in mobile source emissions profiles on the CMB model results. The key parameter impacting model sensitivity was the source profile for gasoline smoker vehicles. High-emitting gasoline smoker vehicles with visible plumes were seen to be a significant source of PM in the area, but use of different measured profiles for smoker vehicles in the model gave very different results for apportionment of gasoline, diesel, and smoker vehicle tailpipe emissions. In addition, the contributions of gasoline and diesel emissions to total ambient PM varied as a function of the site and the day of the week.  相似文献   

3.
ABSTRACT

The chemical mass balance (CMB) model can be applied to estimate the amount of airborne particulate matter (PM) coming from various sources given the ambient chemical composition of the particles measured at the receptor and the chemical composition of the source emissions. Of considerable practical importance is the identification of those chemical species that have a large effect on either the source contributions or errors estimated by the CMB model. This paper details a study of a number of influential diagnostics for application of the CMB software. Some of the diagnostics studied are standard regression diagnostics based on single-row deletion diagnostics. A number of new diagnostics were developed specifically for the CMB application, based on the pseudo-inverse of the source composition matrix and called nondeletion diagnostics to distinguish them from the standard deletion diagnostics. Simulated data sets were generated to compare the diagnostics and their response to controlled amounts of random error.

A particular diagnostic called a modified pseudoinverse matrix (MPIN), developed for this study, was found to be the best choice for CMB model application. The MPIN diagnostic contains virtually all the information present in both deletion and nondeletion diagnostics. Since the MPIN diagnostic requires only the source profiles, it can be used to identify influential species in advance without sampling the ambient data and to improve CMB results through possible remedial actions for the influential species. Specific recommendations are given for interpretation and use of the MPIN diagnostic with the CMB model software. Elements with normalized MPIN absolute values of 1 to 0.5 are associated with influential elements. Noninfluential elements have normalized MPIN absolute values of 0.3 or less. Elements with absolute values between 0.3 and 0.5 are ambiguous but should generally be considered noninfluential.  相似文献   

4.
Abstract

A sensitivity analysis was conducted to characterize sources of uncertainty in results of a molecular marker source apportionment model of ambient particulate matter using mobile source emissions profiles obtained as part of the Gasoline/Diesel PM Split Study. A chemical mass balance (CMB) model was used to determine source contributions to samples of fine particulate matter (PM2.5) collected over 3 weeks at two sites in the Los Angeles area in July 2001. The ambient samples were composited for organic compound analysis by the day of the week to investigate weekly trends in source contributions. The sensitivity analysis specifically examined the impact of the uncertainty in mobile source emissions profiles on the CMB model results. The key parameter impacting model sensitivity was the source profile for gasoline smoker vehicles. High-emitting gasoline smoker vehicles with visible plumes were seen to be a significant source of PM in the area, but use of different measured profiles for smoker vehicles in the model gave very different results for apportionment of gasoline, diesel, and smoker vehicle tailpipe emissions. In addition, the contributions of gasoline and diesel emissions to total ambient PM varied as a function of the site and the day of the week.  相似文献   

5.
Data from two of the United States Environmental Protection Agency's Speciation Trends Network fine particulate matter sites within Chicago, Illinois were used to examine the influence that the results and profiles of the Chemical Mass Balance (CMB) receptor model have on the source contributions and profiles of the Positive Matrix Factorization (PMF) model. This was accomplished using the target shape technique, which utilizes a priori information from the CMB source profiles inputted into the PMF model. The target shape methodology involves inputting specific information for the source profiles into the PMF model as it is resolving source profile and contribution matrices. The target shape results demonstrated it is possible to determine in both the CMB and PMF source profiles those species, which do not influence the solutions of either model.A second method utilizing information from the CMB results was used to impose a condition where the Motor Vehicles source never had a zero contribution as was applied to the CMB model. This involved utilizing an edge rotation to rotate the PMF results to yield a different solution without worsening the fit of the original results. The purpose of this work is to achieve a rotation, which produced a PMF solution where all of the Motor Vehicles contributions were greater than zero. Comparing the rotated Motor Vehicles and Sulfates source contributions in PMF to those obtained from CMB showed a better correlation between the PMF Motor Vehicles contributions to the original CMB results than those prior to rotation.  相似文献   

6.
Ambient particulates of PM2.5 were sampled at three sites in Kaohsiung, Taiwan, during February and March 1999. In addition, resuspended PM2.5 collected from traffic tunnels, paved roads, fly ash of a municipal solid waste (MSW) incinerator, and seawater was obtained. All the samples were analyzed for twenty constituents, including water-soluble ions, organic carbon (OC), elemental carbon (EC), and metallic elements. In conjunction with local source profiles and the source profiles in the model library SPECIATE EPA, the receptor model based on chemical mass balance (CMB) was then applied to determine the source contributions to ambient PM2.5. The mean concentration of ambient PM2.5 was 42.69-53.68 micrograms/m3 for the sampling period. The abundant species in ambient PM2.5 in the mass fraction for three sites were OC (12.7-14.2%), SO4(2-) (12.8-15.1%), NO3- (8.1-10.3%), NH4+ (6.7-7.5%), and EC (5.3-8.5%). Results of CMB modeling show that major pollution sources for ambient PM2.5 are traffic exhaust (18-54%), secondary aerosols (30-41% from SO4(2-) and NO3-), and outdoor burning of agriculture wastes (13-17%).  相似文献   

7.
ABSTRACT

Mobile sources are significant contributors to ambient PM2 5, accounting for 50% or more of the total observed levels in some locations. One of the important methods for resolving the mobile source contribution is through chemical mass balance (CMB) receptor modeling. CMB requires chemically speciated source profiles with known uncertainty to ensure accurate source contribution estimates. Mobile source PM profiles are available from various sources and are generally in the form of weight fraction by chemical species. The weight fraction format is commonly used, since it is required for input into the CMB receptor model. This paper examines the similarities and differences in mobile source PM2.5 profiles that contain data for elements, ions, elemental carbon (EC) and organic carbon (OC), and in some cases speciated organics (e.g., polycyclic aromatic hydrocarbons [PAHs]), drawn from four different sources.

Notable characteristics of the mass fraction data include variability (relative contributions of elements and ions) among supposedly similar sources and a wide range of average EC:OC ratios (0.60 ± 0.53 to 1.42 ± 2.99) for light-duty gasoline vehicles (LDGVs), indicating significant EC emissions from LDGVs in some cases. For diesel vehicles, average EC:OC ratios range from 1.09 ± 2.66 to 3.54 ± 3.07. That different populations of the same class of emitters can show considerable variability suggests caution should be exercised when selecting and using profiles in source apportionment studies.  相似文献   

8.
Source contributions to fine particulate matter in an urban atmosphere   总被引:10,自引:0,他引:10  
Park SS  Kim YJ 《Chemosphere》2005,59(2):217-226
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.  相似文献   

9.
Receptor models are used to identify and quantify source contributions to particulate matter and volatile organic compounds based on measurements of many chemical components at receptor sites. These components are selected based on their consistent appearance in some source types and their absence in others. UNMIX, positive matrix factorization (PMF), and effective variance are different solutions to the chemical mass balance (CMB) receptor model equations and are implemented on available software. In their more general form, the CMB equations allow spatial, temporal, transport, and particle size profiles to be combined with chemical source profiles for improved source resolution. Although UNMIX and PMF do not use source profiles explicitly as input data, they still require measured profiles to justify their derived source factors. The U.S. Supersites Program provided advanced datasets to apply these CMB solutions in different urban areas. Still lacking are better characterization of source emissions, new methods to estimate profile changes between source and receptor, and systematic sensitivity tests of deviations from receptor model assumptions.  相似文献   

10.
Abstract

Receptor models are used to identify and quantify source contributions to particulate matter and volatile organic compounds based on measurements of many chemical components at receptor sites. These components are selected based on their consistent appearance in some source types and their absence in others. UNMIX, positive matrix factorization (PMF), and effective variance are different solutions to the chemical mass balance (CMB) receptor model equations and are implemented on available software. In their more general form, the CMB equations allow spatial, temporal, transport, and particle size profiles to be combined with chemical source profiles for improved source resolution. Although UNMIX and PMF do not use source profiles explicitly as input data, they still require measured profiles to justify their derived source factors. The U.S. Supersites Program provided advanced datasets to apply these CMB solutions in different urban areas. Still lacking are better characterization of source emissions, new methods to estimate profile changes between source and receptor, and systematic sensitivity tests of deviations from receptor model assumptions.  相似文献   

11.
Chemical mass balance (CMB) and trajectory receptor models were applied to speciated particulate matter with aerodynamic diameter < or =2.5 microm (PM2.5) measurements from Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]) and Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring network across the state of Minnesota as part of the Minnesota PM2.5 Source Apportionment Study (MPSAS). CMB equations were solved by the Unmix, positive matrix factorization (PMF), and effective variance (EV) methods, giving collective source contribution and uncertainty estimates. Geological source profiles developed from local dust materials were either incorporated into the EV-CMB model or used to verify factors derived from Unmix and PMF. Common sources include soil dust, calcium (Ca)-rich dust, diesel and gasoline vehicle exhausts, biomass burning, secondary sulfate, and secondary nitrate. Secondary sulfate and nitrate aerosols dominate PM2.5 mass (50-69%). Mobile sources outweigh area sources at urban sites, and vice versa at rural sites due to traffic emissions. Gasoline and diesel contributions can be separated using data from the STN, despite significant uncertainties. Major differences between MPSAS and earlier studies on similar environments appear to be the type and magnitude of stationary sources, but these sources are generally minor (<7%) in this and other studies. Ensemble back-trajectory analysis shows that the lower Midwestern states are the predominant source region for secondary ammoniated sulfate in Minnesota. It also suggests substantial contributions of biomass burning and soil dust from out-of-state on occasions, although a quantitative separation of local and regional contributions was not achieved in the current study. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for a summary of input data, Unmix and PMF factor profiles, and additional maps.  相似文献   

12.
We present estimates of the vehicular contribution to ambient organic carbon (OC) and fine particle mass (PM) in Pittsburgh, PA using the chemical mass balance (CMB) model and a large dataset of ambient molecular marker concentrations. Source profiles for CMB analysis are selected using a method of comparing the ambient ratios of marker species with published profiles for gasoline and diesel vehicle emissions. The ambient wintertime data cluster on a hopanes/EC ratio–ratio plot, and therefore can be explained by a large number of different source profile combinations. In contrast, the widely varying summer ambient ratios can be explained by a more limited number of source profile combinations. We present results for a number of different CMB scenarios, all of which perform well on the different statistical tests used to establish the quality of a CMB solution. The results illustrate how CMB estimates depend critically on the marker-to-OC and marker-to-PM ratios of the source profiles. The vehicular contribution in the winter is bounded between 13% and 20% of the ambient OC (274±56–416±72 ng-C m−3). However, variability in the diesel profiles creates uncertainty in the gasoline–diesel split. On an OC basis, one set of scenarios suggests gasoline dominance, while a second set indicates a more even split. On a PM basis, all solutions indicate a diesel-dominated split. The summer CMB solutions do not present a consistent picture given the seasonal shift and wide variation in the ambient hopanes-to-EC ratios relative to the source profiles. If one set of source profiles is applied to the entire dataset, gasoline vehicles dominate vehicular OC in the winter but diesel dominates in the summer. The seasonal pattern in the ambient hopanes-to-EC ratios may be caused by photochemical decay of hopanes in the summer or by seasonal changes in vehicle emission profiles.  相似文献   

13.
Abstract

Source apportionment analyses were carried out by means of receptor modeling techniques to determine the contribution of major fine particulate matter (PM2.5) sources found at six sites in Mexico City. Thirty-six source profiles were determined within Mexico City to establish the fingerprints of particulate matter sources. Additionally, the profiles under the same source category were averaged using cluster analysis and the fingerprints of 10 sources were included. Before application of the chemical mass balance (CMB), several tests were carried out to determine the best combination of source profiles and species used for the fitting. CMB results showed significant spatial variations in source contributions among the six sites that are influenced by local soil types and land use. On average, 24-hr PM2.5 concentrations were dominated by mobile source emissions (45%), followed by secondary inorganic aerosols (16%) and geological material (17%). Industrial emissions representing oil combustion and incineration contributed less than 5%, and their contribution was higher at the industrial areas of Tlalnepantla (11%) and Xalostoc (8%). Other sources such as cooking, biomass burning, and oil fuel combustion were identified at lower levels. A second receptor model (principal component analysis, [PCA]) was subsequently applied to three of the monitoring sites for comparison purposes. Although differences were obtained between source contributions, results evidence the advantages of the combined use of different receptor modeling techniques for source apportionment, given the complementary nature of their results. Further research is needed in this direction to reach a better agreement between the estimated source contributions to the particulate matter mass.  相似文献   

14.
Receptor-based chemical mass balance (CMB) analysis techniques are designed to apportion species that are conserved during pollutant transport using conserved source profiles. The techniques will fail if non-conservative species (or profiles) are not properly accounted for in the CMB model. The straightforward application of the CMB model developed for Project MOHAVE using regional profiles resulted in a significant under-prediction of total sulfate oxides (SOx, SO2 plus fine particulate sulfate) for many samples at Meadview, AZ. In addition, for these samples the concentration of the inert tracer emitted from the MOHAVE Power Project (MPP), ocPDCH, was also under-predicted. A second-generation model has been developed which assumes that separation of particles and SO2 can occur in the MPP plume during nighttime stable plume conditions. This second-generation CMB model accounts for all SOx present at the various receptor sites. In addition, the concentrations of ocPDCH and the presence of other inert tracers of emission from regional sources are accurately predicted. The major source of SOx at Meadview was the MPP, but the major source of sulfate at this site was the Las Vegas urban area. At Hopi Point in the Grand Canyon, the Baja California region (Imperial Valley and northwestern Mexico) was the major source of both SOx and sulfate.  相似文献   

15.
The methods of positive matrix factorization–chemical mass balance and principal component analysis/multiple linear regression–chemical mass balance were studied in this paper, for combined source apportionment. Due to the high similarity among the source profiles, several problems would raised when only one receptor model was applied. For example, the collinearity problem would result in the negative contributions when applying CMB model; certain sources would not to be separated out when applying PCA or PMF model. In this study, PCA/MLR–CMB model and PMF–CMB were attempted to resolve the problem, where the combined models were applied to study the synthetic and ambient datasets. In synthetic dataset, there were seven sources (six actual sources from real world, and one unknown source). The results obtained by the combined models show that the combined source apportionment technique is feasible. In addition, an ambient dataset from a northern city in China was analyzed by PCA/MLR–CMB model and PMF–CMB model, and these two models got the similar results. The results show that coal combustion contributed the largest fraction to the total mass.  相似文献   

16.
To investigate the chemical characteristics of fine particles in the Sihwa area, Korea, atmospheric aerosol samples were collected using a dichotomous PM10 sampler and two URG PM2.5 cyclone samplers during five intensive sampling periods between February 1998 and February 1999. The Inductively Coupled Plasma (ICP)-Atomic Emission Spectrometry (AES)/ICP-Mass Spectrometry (MS), ion chromatograph (IC), and thermal manganese dioxide oxidation (TMO) methods were used to analyze the trace elements, ionic species, and carbonaceous species, respectively. Backward trajectory analysis, factor analysis, and a chemical mass balance (CMB) model were used to estimate quantitatively source contributions to PM2.5 particles collected in the Sihwa area. The results of PM2.5 source apportionment using the CMB7 receptor model showed that (NH4)2SO4 was, on average, the major contributor to PM2.5 particles, followed by nontraffic organic carbon (OC) emission, NH4NO3, agricultural waste burning, motor vehicle emission, road dust, waste incineration, marine aerosol, and others. Here, the nontraffic OC sources include primary anthropogenic OC emitted from the industrial complex zone, secondary OC, and organic species from distant sources. The source impact of waste incineration emission became significant when the dominant wind directions were from southwest and west sectors during the sampling periods. It was found that PM2.5 particles in the Sihwa area were influenced mainly by both anthropogenic local sources and long-range transport and transformation of air pollutants.  相似文献   

17.
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".  相似文献   

18.
Abstract

Chemical mass balance receptor models (CMBs) use measured pollutant concentrations, along with source information, to apportion the contributions of primary sources to the measured concentrations. CMBs can be used to evaluate the accuracy of the emission inventories that underlie State Implementation Plan (SIP) modeling, by providing an allocation of emissions to individual source categories. CMBs, however, traditionally have not accounted for the chemical reaction and differential deposition or fractionation that occur between the source and receptor. This means that they have historically had severe limitations in apportioning secondary particulate matter (PM), which is an especially important component of fine PM (PM2.5). Stafford and Liljestrand developed a method to account for fractionation in CMBs using depletion factors based on a solution of the steady-state advection-dispersion equation, including gravitational settling, dry deposition, and first-order chemical reaction. In the research presented here, the method of Stafford and Liljestrand was tested using gaseous and PM ambient concentration data from the Los Angeles, CA, air shed, along with traffic source profiles specific to Los Angeles and the CMB7 receptor model of the U.S. Environment Protection Agency. Including fractionation increased nitrate apportioned from 5% and 6% to 83% and 86% for Claremont, CA, and Long Beach, CA, respectively. This is significant, because CMBs have historically had difficulty apportioning nitrate. Including fractionation increased the ammonium apportioned by a factor of 7. The method could be used in future case studies to apportion secondary organic carbon as well.  相似文献   

19.
Source apportionment with site specific source profiles   总被引:1,自引:0,他引:1  
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.  相似文献   

20.
Street sweeping is often proposed as a means of reducing the emissions from paved roads. The objective of this study was to evaluate the effectiveness of street sweeping on ambient particulate matter concentrations and to determine the difference In source contributions to PM10 concentrations between street sweeping and non-street sweeping periods.

Chemically-speciated measurements of PM10 and PM2.5 were taken in the commercial section of Reno, Nevada, for a one-month sampling period. The Chemical Mass Balance (CMB) model was applied to these data and an average of approximately 50 percent of the PM10 was apportioned to resuspended geological material. During half of the sampling period, streets In the vicinity of the sampling site were completely swept with a regenerative-air vacuum sweeper, while no sweeping was performed during the remainder of the experiment. Ratios of primary geological contributions divided by primary motor vehicle contributions to PM10 were compared between sweeping and non-sweeping periods using analysis of variance. This ratio of source contributions minimizes the effects of variations in traffic volume and meteorological dispersion. No significant differences in geological contributions to PM10 were detected as a result of regenerative-air vacuum street sweeping.  相似文献   

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