Origins of primary and secondary organic aerosol in Atlanta: results of time-resolved measurements during the Atlanta Supersite Experiment

Time-resolved ambient particulate organic (OC) and elemental carbon (EC) data measured in Atlanta, GA, during the Atlanta Supersite Experiment (August3-September 1, 1999) were investigated to determine the temporal trends of atmospheric carbonaceous aerosol and to examine the relative contributions of primary and secondary OC to measured particulate OC. Mean 1-h average concentrations (ranges in parentheses) of PM2.5 OC, EC, and total carbon were 8.3 (3.6-15.8), 2.3 (0.3-9.6), and 10.6 (4.6-24.6) microg of C m(-3), respectively, based on Rutgers University/Oregon Graduate Institute in situ thermal-optical carbon analyzer measurements. Carbonaceous matter (organic material 40%; EC 8%) comprised approximately 48% of PM2.5 mass in Atlanta. Primary and secondary OC concentrations were estimated using an EC tracer method. Secondary OC contributed approximately 46% of measured particulate OC, and 1-h average contributions ranged up to 88%. Vehicle emissions appear to be the dominant contributors to measured EC and primary OC concentrations based on temporal patterns of EC, primary OC, and CO. This research suggests that secondary OC concentrations in Atlanta were influenced by (1) "fresh" secondary organic aerosol formed by photochemical reactions locally in the early afternoons as seen in the Los Angeles air basin and (2) "aged" secondary organic aerosol transported from upwind regions or formed on previous days. Nocturnal peaks in secondary OC and ozone concentrations were observed on several days. The most probable explanation for this is the favorable partitioning of semivolatile organic compounds to the particulate phase driven by temperature decreases and relative humidity increases at night and vertical transport of regional pollutants from above to ground level.     

Spatial variability of carbonaceous aerosol concentrations in East and West Jerusalem

Carbonaceous aerosol concentrations and sources were compared during a year long study at two sites in East and West Jerusalem that were separated by a distance of approximately 4 km. One in six day 24-h PM(2.5) elemental and organic carbon concentrations were measured, along with monthly average concentrations of particle-phase organic compound tracers for primary and secondary organic aerosol sources.Tracer compounds were used in a chemical mass balance ICMB) model to determine primary and secondary source contributions to organic carbon. The East Jerusalem sampling site at Al Quds University experienced higher concentrations of organic carbon (OC) and elemental carbon (EC) compared to the West Jerusalem site at Hebrew University. The annual average concentrations of OC and EC at the East Jerusalem site were 5.20 and 2.19 μg m(-3), respectively, and at the West Jerusalem site were 4.03 and 1.14 μg m(-3), respectively. Concentrations and trends of secondary organic aerosol and vegetative detritus were similar at both sites, but large differences were observed in the concentrations of organic aerosol from fossil fuel combustion and biomass burning, which was the cause of the large differences in OC and EC concentrations observed at the two sites.     

Intercomparison of thermal-optical methods for the determination of organic and elemental carbon: influences of aerosol composition and implications

An intercomparison of organic carbon (OC) and elemental carbon (EC) measurements was conducted based on ambient aerosol samples collected during four seasons in Beijing, China. Dependence of OC and EC values on the temperature protocol and the charring correction method is presented and influences of aerosol composition are investigated. EC was found to decrease with the peak inert mode temperature (T(peak)) such that EC determined by the IMPROVE (the Interagency Monitoring of Protected Visual Environments)-A protocol (T(peak) was 580 °C) was 2.85 ± 1.31 and 3.83 ± 2.58 times that measured by an alternative protocol with a T(peak) of 850 °C when using the transmittance and reflectance correction, respectively. It was also found that reflectance correction tends to classify more carbon as EC compared with transmittance; results from the IMPROVE-A protocol showed that the ratio of EC defined by reflectance correction (EC(R)) to that based on transmittance (EC(T)) averaged 1.50 ± 0.42. Moreover, it was demonstrated that emissions from biomass burning would increase the discrepancy between EC values determined by different temperature protocols. On the other hand, the discrepancy between EC(R) and EC(T) was strongly associated with secondary organic aerosol (SOA) which was shown to be an important source of the organics that pyrolyze during the inert mode of thermal-optical analysis.     

Formation of aerosol particles from reactions of secondary and tertiary alkylamines: characterization by aerosol time-of-flight mass spectrometry

In ambient field studies conducted with aerosol time-of-flight mass spectrometry (ATOFMS), individual particle mass spectra commonly contain ion peaks at mass/charge (m/z) 86, 101, 102, and 118. Particles with mass spectra containing these peaks show a strong correlation with high relative humidity and low temperatures. In an effort to identify these peaks, a series of smog chamber studies were conducted probing the chemistry of secondary and tertiary alkylamines. Specifically, in separate studies, trimethylamine, di- and triethylamine, and di- and tripropylamine were reacted in a 1 m3 Teflon outdoor smog chamber with naturally occurring levels of gas phase oxidants in ambient air. The aerodynamic sizes and individual mass spectra of the resulting aerosol particles were acquired continuously using aerosol time-of-flight mass spectrometry (ATOFMS). Both oxidation and acid-base reactions between amines and acids commonly present in the atmosphere (i.e., nitric and sulfuric acid) appear to play roles in the formation and chemistry of organic nitrogen-containing particle phase species. Ion peaks in the individual particle mass spectra indicate the presence of alkyl ammonium salts, as well as other tentatively identified organic N-containing compounds formed by oxidation processes. Also, for the first time, tertiary alkylamine-N-oxides have been identified as alkylamine oxidation products in the aerosol particle phase. Smog chamber reactions involving triethylamine produce ATOFMS mass spectra with similar ion peak combinations as those observed in the spectra of particles commonly detected in ambient and vehicular source characterization studies. The results of this study suggest that amine chemistry involving gas-to-particle conversion and photooxidation processes may play a significant role in particle formation in regions with high amine concentrations.     

Evaluation of an air quality model for the size and composition of source-oriented particle classes

Air quality model predictions of the size and composition of atmospheric particle classes are evaluated by comparison with aerosol time-of-flight mass spectrometry (ATOFMS) measurements of single-particle size and composition at Long Beach and Riverside, CA, during September 1996. The air quality model tracks the physical diameter, chemical composition, and atmospheric concentration of thousands of representative particles from different emissions classes as they are transported from sources to receptors while undergoing atmospheric chemical reactions. In the model, each representative particle interacts with a common gas phase but otherwise evolves separately from all other particles. The model calculations yield an aerosol population, in which particles of a given size may exhibit different chemical compositions. ATOFMS data are adjusted according to the known particle detection efficiencies of the ATOFMS instruments, and model predictions are modified to simulate the chemical sensitivities and compositional detection limits of the ATOFMS instruments. This permits a direct, semiquantitative comparison between the air quality model predictions and the single-particle ATOFMS measurements to be made. The air quality model accurately predicts the fraction of atmospheric particles containing sodium, ammonium, nitrate, carbon, and mineral dust, across all particle sizes measured by ATOFMS at the Long Beach site, and in the coarse particle size range (Da > or = 1.8 microm) atthe Riverside site. Given thatthis model evaluation is very likely the most stringent test of any aerosol air quality model to date, the model predictions show impressive agreement with the single-particle ATOFMS measurements.     

Uncertainties in charring correction in the analysis of elemental and organic carbon in atmospheric particles by thermal/optical methods

Thermal/optical methods are widely used in the determination of aerosol organic carbon (OC) and elemental carbon (EC) collected on quartz filters. A fraction of OC undergoes charring to form pyrolytically generated EC (PEC) during thermal analysis. The correct speciation of OC and EC in thermaVoptical methods depends on one of the following two assumptions: (1) PEC evolves before native EC evolves in the analysis or (2) PEC and native EC have the same apparent light absorption coefficient (sigma) at the monitoring light wavelength. Neither of these assumptions has actually ever been checked or tested. The first assumption is invalidated by the observation that the combustion of PEC overlaps that of native EC despite multiple stepwise combustion at temperatures ranging from 575 to 910 degrees C. An examination of sigma versus EC evolution indicates that the sigma values of PEC and EC are not the same in most cases and the a value of PEC is not constant during a single thermal analysis. The second assumption is thus invalid as well. The measured EC concentrations can either overestimate or underestimate the true native EC concentrations depending on the relative magnitude of the a values of the PEC and native EC at the point where the instrument sets the EC/OC split line. Both over- and underestimation have been observed in real aerosol samples. The unequal a values of PEC and EC also explain that different temperature programs, when employed to analyze the same filter samples, systematically yield different EC and OC concentrations. Our findings imply that minimizing charring improves the accuracy of the EC/OC split in thermal/optical methods.     

Determination of single particle mass spectral signatures from light-duty vehicle emissions

In this study, 28 light-duty gasoline vehicles (LDV) were operated on a chassis dynamometer at the California Air Resources Board Haagen-Smit Facility in El Monte, CA. The mass spectra of individual particles emitted from these vehicles were measured using aerosol time-of-flight mass spectrometry (ATOFMS). A primary goal of this study involves determining representative size-resolved single particle mass spectral signatures that can be used in future ambient particulate matter source apportionment studies. Different cycles were used to simulate urban driving conditions including the federal testing procedure (FTP), unified cycle (UC), and the correction cycle (CC). The vehicles were selected to span a range of catalytic converter (three-way, oxidation, and no catalysts) and engine technologies (vehicles models from 1953 to 2003). Exhaust particles were sampled directly from a dilution and residence chamber system using particle sizing instruments and an ATOFMS equipped with an aerodynamic lens (UF-ATOFMS) analyzing particles between 50 and 300 nm. On the basis of chemical composition, 10 unique chemical types describe the majority of the particles with distinct size and temporal characteristics. In the ultrafine size range (between 50 and 100 nm), three elemental carbon (EC) particle types dominated, all showing distinct EC signatures combined with Ca, phosphate, sulfate, and a lower abundance of organic carbon (OC). The relative fraction of EC particle types decreased as particle size increased with OC particles becoming more prevalent above 100 nm. Depending on the vehicle and cycle, several distinct OC particle types produced distinct ion patterns, including substituted aromatic compounds and polycyclic aromatic hydrocarbons (PAH), coupled with other chemical species including ammonium, EC, nitrate, sulfate, phosphate, V, and Ca. The most likely source of the Ca and phosphate in the particles is attributed to the lubricating oil. Significant variability was observed in the chemical composition of particles emitted within the different car categories as well as for the same car operating under different driving conditions. Two-minute temporal resolution measurements provide information on the chemical classes as they evolved during the FTP cycle. The first two minutes of the cold start produced more than 5 times the number of particles than any other portion of the cycle, with one class of ultrafine particles (EC coupled with Ca, OC, and phosphate) preferentially produced. By number, the three EC with Ca classes (which also contained OC, phosphate, and sulfate) were the most abundant classes produced by the nonsmoking vehicles. The smoker category produced the highest number of particles, with the dominant classes being OC comprised of substituted monoaromatic compounds and PAHs, coupled with Ca and phosphate, thus suggesting used lubricating oil was associated with many of these particles. These studies show, by number, EC particles dominate gasoline emissions in the ultrafine size range particularlyforthe lowest emitting newer vehicles, suggesting the EC signature alone cannot be used as a unique tracer for diesels. This represents the first report of high time- and size-resolved chemical composition data showing the mixing state of nonrefractory elements in particles such as EC for vehicle emissions during dynamometer source testing.     

Semicontinuous measurements of organic carbon and acidity during the Pittsburgh Air Quality Study: implications for acid-catalyzed organic aerosol formation

Laboratory evidence suggests that inorganic acid seed particles may increase secondary organic aerosol yields secondary organic aerosol (SOA) through heterogeneous chemistry. Additional laboratory studies, however, report that organic acidity generated in the same photochemical process by which SOA is formed may be sufficient to catalyze these heterogeneous reactions. Understanding the interaction between inorganic acidity and SOA mass is important when evaluating emission controls to meet PM2.5 regulations. We examine semicontinuous measurements of organic carbon (OC), elemental carbon (EC), and inorganic species from the Pittsburgh Air Quality Study to determine if we can detect coupling in the variations of inorganic acidity and OC. We were not able to detect significant enhancements of SOA production due to inorganic acidity in Western Pennsylvania most of the time, but its signal might have been lost in the noise. If we assume a causal relationship between inorganic acidity and OC, reductions in OC for Western Pennsylvania that might result from drastic reductions in inorganic acidity were estimated to be 2 +/- 4% by a regression technique, and an upper bound for this geographic area was estimated to be 5 +/- 8% based on calculations from laboratory measurements.     

ACE-Asia intercomparison of a thermal-optical method for the determination of particle-phase organic and elemental carbon

A laboratory intercomparison of organic carbon (OC) and elemental carbon (EC) measurements of atmospheric particulate matter samples collected on quartz filters was conducted among eight participants of the ACE-Asia field experiment The intercomparison took place in two stages: the first round of the intercomparison was conducted when filter samples collected during the ACE-Asia experiment were being analyzed for OC and EC, and the second round was conducted after the ACE-Asia experiment and included selected samples from the ACE-Asia experiment Each participant operated ECOC analyzers from the same manufacturer and utilized the same analysis protocol for their measurements. The precision of OC measurements of quartz fiber filters was a function of the filter's carbon loading but was found to be in the range of 4-13% for OC loadings of 1.0-25 microg of C cm(-2). For measurements of EC, the precision was found to be in the range of 6-21% for EC loadings in the range of 0.7-8.4 microg of C cm(-2). It was demonstrated for three ambient samples, four source samples, and three complex mixtures of organic compounds that the relative amount of total evolved carbon allocated as OC and EC (i.e., the ECOC split) is sensitive to the temperature program used for analysis, and the magnitude of the sensitivity is dependent on the types of aerosol particles collected. The fraction of elemental carbon measured in wood smoke and an extract of organic compounds from a wood smoke sample were sensitive to the temperature program used for the ECOC analysis. The ECOC split for the three ambient samples and a coal fly ash sample showed moderate sensitivity to temperature program, while a carbon black sample and a sample of secondary organic aerosol were measured to have the same split of OC and EC with all temperature programs that were examined.     

Chemical investigation of eight different types of carbonaceous particles using thermoanalytical techniques

The chemical composition of ambient aerosol particles affects numerous important aerosol parameters such as their hygroscopicity, optics, and mass as well as their potentially adverse health effects. The objective of this study was to derive both detailed chemical speciation and useful proxies for the quantitative classification of the organic matter (OM) content of carbonaceous aerosol samples. Using three different thermal desorption techniques in an inert atmosphere we investigated eight different carbonaceous particulate matter (PM) samples used for health effect studies: thermal desorption gas chromatography with mass spectrometry, evolved gas analysis with mass spectrometry, and thermogravimetry with Fourier transform infrared spectroscopy. The samples include different types of laboratory-generated particles (pigment black, diffusion flame soot, spark-generated carbon) and two ambient aerosol samples (diesel soot and particulates collected in a road tunnel). All samples showed increasing mass desorption with rising temperature, but no reliable OM classification was possible based on thermal mass desorption alone. In fact, the "organic-free" spark-generated carbon particles showed the second highest mass desorption at 800 degrees C due to the formation of oxygenated structures on unsaturated surface sites and the subsequent evolution of CO and CO2 at elevated temperatures. A quantitative OM classification was accomplished by combining measurements of thermogravimetry and mass spectrometry (up to 800 degrees C) into a novel parameter, the "apparent organic mass fraction". The validity of this classification was confirmed with a second proxy parameter, based only on the evolution of organic components during thermal desorption and information on the generation process of the particles. Both types of pigment blacks (Printex) samples and the spark-generated carbon particles showed the lowest apparent organic mass fraction (< 5%), whereas for road tunnel and diesel emission particles < 16 and < 19% was estimated, respectively.     

Study of the effects of particle-phase carbon on the gas/particle partitioning of semivolatile organic compounds in the atmosphere using controlled field experiments

A controlled field experiment (CFE) methodology with a filter/sorbent sampler was used to minimize artifact effects when measuring values of the gas/particle (G/P) partitioning constant (Kp, m3 microg(-1)) for semivolatile organic compounds (SOCs) in the atmosphere. CFE sampling was conducted at three different locations (Beaverton, OR; Denver, CO; and Hills, IA). Kp values were measured for a series of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs). To examine the possible effects on the G/P partitioning of the amounts of organic material (om) phase, organic carbon (OC), and elemental carbon (EC) in the sampled particulate material, the measured Kp values were normalized by the aerosol mass fractions f(om), f(OC), and f(EC) according to Kp/ f(om), Kp/f(OC), and Kp/f(EC). Using a log-log format, the resulting normalized values were all found to be more highly correlated with the subcooled liquid vapor pressure p(L)o than were the unnormalized Kp values. For the PAHs,the one-parameter model assuming Kp = Kp,OC f(OC) yielded only slightly less variability in the predicted Kp values than did the one-parameter model Kp = Kp,EC f(EC). The two-parameter model Kp = Kp,OC f(OC) + Kp,EC f(EC) was found to provide only small improvements over each of the one-parameter models. Overall, the data are more consistent with an absorptive mechanism of partitioning to the particulate material but do not rule out some role for adsorption to particle surfaces. The data suggest that small amounts of organic carbon (f(OC) approximately 0.02) can have significant effects on the G/P partitioning of SOCs.     

Size distribution characteristics of elemental carbon emitted from Chinese vehicles: results of a tunnel study and atmospheric implications

The size distribution characteristics of elemental carbon (EC) emissions from Chinese vehicles have not been previously described. In this study, we collected size-segregated aerosol samples using a 10-stage MOUDI sampler (0.056-18 microm) in the Zhujiang tunnel, a roadway tunnel in the urban area of Guangzhou, China. The samples were analyzed for EC, organic carbon (OC), and inorganic ions. Fine particles had an OC/EC ratio of 0.57, indicating a dominant contribution of EC from diesel vehicles. Both EC and OC showed a dominant accumulation mode with a mass median aerodynamic diameter (MMAD) of 0.42 microm. In comparison, studies available in the literature typically reported a much lower MMAD for EC (approximately 0.1 microm) in vehicular emissions in North America. A theoretical analysis indicated that the larger EC particles observed in this study could not have resulted from after-emission growth processes (i.e., water accretion, coagulation, and vapor condensation). This leaves operating conditions such as high engine loads and low combustion efficiencies, which are more prevalent in diesel-fueled Chinese vehicles, as a more plausible inherent reason for producing the larger EC agglomerates. While fresh 0.1 microm EC particles are unlikely to act as cloud condensation nuclei (CCN), calculations showed that EC particles as large as 0.42 microm are effective CCN at atmospherically relevant critical supersaturation values of less than 1%. As a result, fresh EC particles from Chinese vehicle emissions could readily undergo cloud processing and form internal mixtures with sulfate in the residue droplet mode particles. This prediction is consistent with observations that EC frequently showed a dominant droplet mode in urban atmospheres in this region. The internal mixing of EC with highly hygroscopic sulfate would facilitate its removal by wet deposition and shorten its lifetime in the atmosphere. In addition, the light-absorbing capabilities of EC particles could also be enhanced due to their internal mixing with sulfate. Numerical aerosol models need to take these factors into consideration for better predictions of the behaviors and effects of urban aerosols in China.     

Source attribution of submicron organic aerosols during wintertime inversions by advanced factor analysis of aerosol mass spectra

Real-time measurements of submicrometer aerosol were performed using an Aerodyne aerosol mass spectrometer (AMS) during three weeks at an urban background site in Zurich (Switzerland) in January 2006. A hybrid receptor model which incorporates a priori known source composition was applied to the AMS highly time-resolved organic aerosol mass spectra. Three sources and components of submicrometer organic aerosols were identified: the major component was oxygenated organic aerosol (OOA), mostly representing secondary organic aerosol and accounting on average for 52-57% of the particulate organic mass. Radiocarbon (14C) measurements of organic carbon (OC) indicated that approximately 31 and approximately 69% of OOA originated from fossil and nonfossil sources, respectively. OOA estimates were strongly correlated with measured particulate ammonium. Particles from wood combustion (35-40%) and 3-13% traffic-related hydrocarbon-like organic aerosol (HOA) accounted for the other half of measured organic matter (OM). Emission ratios of modeled HOA to measured nitrogen oxides (NOx) and OM from wood burning to levoglucosan from filter analyses were found to be consistent with literature values.     

Charring characteristics of atmospheric organic particulate matter in thermal analysis

The charring of organic materials during carbon analysis bythermal methods makes it difficult to differentiate elemental carbon (EC) from organic carbon (OC). Failure to correct for charring results in the overestimation of EC and the underestimation of OC. The charring characteristics andthermal behaviors of aerosol OC are studied by subjecting hexane and water extracts of ambient aerosols to various analysis conditions. The complete evolution of water-soluble organic carbon (WSOC) aerosol materials is found to require a temperature as high as 850 degrees C and the presence of oxygen. EC would be oxidized under these thermal conditions as well. As a result, thermal methods relying only on temperature for the differentiation of EC and OC would give unreliable OC and EC concentrations. Our investigation also reveals that WSOC accounts for a large fraction (13-66%) of charring, while hexane extractable organic compounds produce little charring. The extent of charring from WSOC, defined as the ratio between pyrolytically generated EC to the total WSOC, is found to increase with the WSOC loading in each analysis when the loadings are below a certain value. This ratio remains constant when the loadings are above this value. This may account for the high variability in the extent of charring among aerosol samples from different locations as well as among samples from a single location collected at different times. Charring is reduced if the residence time at each temperature step in a helium atmosphere is sufficiently long to allow for maximum C evolution at each step. Charring is also influenced by the presence of inorganic constituents such as ammonium bisulfate. For the few tested organic materials, it is observed that ammonium bisulfate enhances the charring of starch and cellulose but reduces the charring of levoglucosan.     

Sorption of a diverse set of organic vapors to diesel soot and road tunnel aerosols

In a traffic-dominated environment sorption of organic pollutants to exhaust aerosols can strongly determine their further fate. The sorption properties of two aerosol samples representing different exhaust sources have been determined for a large set of diverse organic vapors. For pure diesel soot we could identify adsorption to elemental carbon (EC) as the dominant sorption process. We used our experimental equilibrium adsorption coefficients to derive a predictive model for adsorption on soot in line with adsorption models for other surfaces published earlier. On road tunnel aerosols, both adsorption to EC and absorption in organic matter (OM) governed the observed sorption and the data could not be further evaluated in terms of a specific sorption mechanism.     

Single particle characterization of ultrafine and accumulation mode particles from heavy duty diesel vehicles using aerosol time-of-flight mass spectrometry

The aerodynamic size and chemical composition of individual ultrafine and accumulation mode particle emissions (Da = 50-300 nm) were characterized to determine mass spectral signatures for heavy duty diesel vehicle (HDDV) emissions that can be used for atmospheric source apportionment. As part of this study, six in-use HDDVs were operated on a chassis dynamometer using the heavy heavy-duty diesel truck (HHDDT) five-cycle driving schedule under different simulated weight loads. The exhaust emissions were passed through a dilution/residence system to simulate atmospheric dilution conditions, after which an ultrafine aerosol time-of-flight mass spectrometer (UF-ATOFMS) was used to sample and characterize the HDDV exhaust particles in real-time. This represents the first study where refractory species including elemental carbon and metals are characterized directly in HDDV emissions using on-line mass spectrometry. The top three particle classes observed with the UF-ATOFMS comprise 91% of the total particles sampled and show signatures indicative of a combination of elemental carbon (EC) and engine lubricating oil. In addition to the vehicle make/year, the effects of driving cycle and simulated weight load on exhaust particle size and composition were investigated.     

Using aerosol light absorption measurements for the quantitative determination of wood burning and traffic emission contributions to particulate matter

A source apportionment study was performed for particulate matter in the small village of Roveredo, Switzerland, where more than 70% of the households use wood burning for heating purposes. A two-lane trans-Alpine highway passes through the village and contributes to the total aerosol burden in the area. The village is located in a steep Alpine valley characterized by strong and persistent temperature inversions during winter, especially from December to February. During two winter and one early spring campaigns, a seven-wavelength aethalometer, high volume (HIVOL) samplers, an Aerodyne quadrupole aerosol mass spectrometer (AMS), an optical particle counter (OPC), and a Sunset Laboratory OCEC analyzer were deployed to study the contribution of wood burning and traffic aerosols to particulate matter. A linear regression model of the carbonaceous particulate mass in the submicrometer size range CM(PM1) as a function of aerosol light absorption properties measured by the aethalometer is introduced to estimate the particulate mass from wood burning and traffic (PM(wb), PM(traffic)). This model was calibrated with analyses from the 14C method using HIVOL filter measurements. These results indicate that light absorption exponents of 1.1 for traffic and 1.8-1.9 for wood burning calculated from the light absorption at 470 and 950 nanometers should be used to obtain agreement of the two methods regarding the relative wood burning and traffic emission contributions to CM(PM1) and also to black carbon. The resulting PM(wb) and PM(traffic) values explain 86% of the variance of the CM(PM1) and contribute, on average, 88 and 12% to CM(PM1), respectively. The black carbon is estimated to be 51% due to wood burning and 49% due to traffic emissions. The average organic carbon/total carbon (OC/TC) values were estimated to be 0.52 for traffic and 0.88 for wood burning particulate emissions.     

Source apportionment of fine particulate matter by clustering single-particle data: tests of receptor model accuracy

The source apportionment accuracy of a neural network algorithm (ART-2a) is tested on the basis of its application to synthetic single-particle data generated by a source-oriented aerosol processes trajectory model that simulates particle emission, transport, and chemical reactions in the atmosphere. ART-2a successfully groups particles from the majority of sources actually present, when given complete data on ambient particle composition at monitoring sites located near the emission sources. As particles age in the atmosphere, accumulation of gas-to-particle conversion products can act to disguise the source of the primary core of the particles. When ART-2a is applied to synthetic single-particle data that are modified to simulate the biases in aerosol time-of-flight mass spectrometry (ATOFMS) measurements, best results are obtained using the ATOFMS dual ion operating mode that simultaneously yields both positive and negative ion mass spectra. The results of this study suggest that the use of continuous single-particle measurements coupled with neural network algorithms can significantly improve the time resolution of particulate matter source apportionment.     

Comparison of carbonaceous aerosols in Tokyo before and after implementation of diesel exhaust restrictions

We compared the status of carbonaceous aerosols in Tokyo before and after the implementation of a diesel vehicle regulation intended to reduce the quantity of particulate carbon from diesel engines in one of the largest scale ever attempts at vehicle exhaust control. Radiocarbon (14C) in elemental carbon (EC) and total carbon (TC) were analyzed to identify fossil fuel carbonaceous particles emitted from diesel-powered vehicles. One-sided paired-month t-tests showed no distinct difference in the absolute concentrations of particles in terms of total mass (19.5 to 18.0 microg m(-3); p = 0.321), EC (3.6 to 3.3 microg m(-3); p = 0.272), and TC (6.3 to 6.2 microg m(-3); p = 0.418) for the finest particles (d(a) < 1.1 microm) after the implementation of the regulation. The ratios of the concentrations of the chemical constituents were, however, altered after the regulation. EC/TC was significantly decreased from 56.7% to 50.2% (p = 0.039). Although it was not statistically significant, the percentage of fossil carbon in EC also decreased (67.8% to 63.8%; p = 0.104). Since EC is predominantly of combustion origin, the observed decrease was likely due to the decrease in fossil EC emissions from diesel-powered vehicles. The decrease in EC/TC after the implementation of the regulation was also likely to have resulted from attachment to diesel vehicle exhaust systems of particulate filters as required as part of the regulation by the Tokyo Metropolitan Government. The EC/TC of fossil carbon of the finest particles decreased from 66.2% to 55.2% (p = 0.066), but EC/TC of biomass carbon did not decrease but rose slightly from 43.6% to 44.5% (p > 0.5). Thus, the relative ratios of components of carbonaceous aerosol particles, such as 14C, could provide a better understanding of the atmospheric pollution status, despite short-term fluctuations, than do measurements of absolute concentrations.