Determination and comparison of nitrated-polycyclic aromatic hydrocarbons measured in air and diesel particulate reference materials

The National Institute of Standards and Technology has issued numerous environmental matrix standard reference materials (SRMs) for the measurement of polycyclic aromatic hydrocarbons; however, only one SRM (diesel particulate material) was issued with certified and reference values for four nitrated-polycyclic aromatic hydrocarbons (nitro-PAH). The objective of this study was to develop an improved analytical procedure to quantify 28 mononitro- and dinitro-PAHs, including numerous isomers, in air and diesel particulate SRMs. Two air particulate matrix SRMs, SRM 1649a Urban Dust and SRM 1648 Urban Particulate Matter, and fine particulate matter, collected from Baltimore MD for use as an "interim reference material" for the determination of organic contaminants, have been characterized for nitro-PAHs. Concentrations of nitro-PAHs in all three air particulate materials were at the ng/g level with the highest nitro-PAH concentration being 2-nitrofluoranthene (range between 246 and 340 ng/g). For the three diesel particulate-related SRMs, SRM 1650a Diesel Particulate Matter, SRM 1975 Diesel Particulate Extract, and SRM 2975 Diesel Particulate Matter (Industrial Fortlift), concentrations of nitro-PAHs were in the microg/g range, with 1-nitropyrene as the dominant nitro-PAH (range between 18 and 40 microg/g). Distinct nitro-PAH isomer patterns were present between the air and diesel particulate materials. These results will provide isomer identification and reference concentrations for a large number of nitro-PAHs in the existing diesel and air particulate SRMs. Published by Elsevier Science Ltd.     

Selective and sensitive analysis of nitro-PAH

Nitro-containing polycyclic aromatic hydrocarbons (nitro-PAH) were reduced to the corresponding amino-PAH and derivatised with heptafluorobutyric anhydride (HFBA) prior to analysis by gas chromatography and negative ion chemical ionisation mass spectrometry (GC/NCIMS). The sensitivity was improved up to 6 times compared to analysis by GC/NCIMS of the underivatised nitro-PAH. A clean-up procedure suitable for complex nitro-PAH containing samples was developed. More than ninety nitro-PAH were indicated in a particulate extract from a diesel automobile exhaust sample.     

Comparison of vehicle exhaust emissions from modified diesel fuels

Three diesel fuels, one oil sand-derived (OSD) diesel serving as base fuel, one cetane-enhanced base fuel, and one oxygenate [diethylene glycol dimethyl ether (DEDM)]-blended base fuel, were tested for their emission characterizations in vehicle exhaust on a light-duty diesel truck that reflects the engine technology of the 1994 North American standard. Both the cetane-enhanced and the oxygenate-blended fuels were able to reduce regulated [CO, particulate matter (PM), total hydrocarbon (THC)] and nonregulated [polyaromatic hydrocarbons (PAHs), carbonyls, and other volatile organic chemicals] emissions, except for nitrogen oxides (NO(x)), compared with the base fuel. Although burning a fuel that contains oxygen could conceivably yield more oxygenated compounds in emissions, the oxygenate-blended diesel fuel resulted in reduced emissions of formaldehyde along with hydrocarbons such as benzene, 1,3-butadiene, and PAHs. Reductions in nitro-PAH emissions have been observed in both the cetane-enhanced and oxygenated fuels. This further demonstrates the benefits of using a cetane enhancer and the oxygenated fuel component.     

Emission rates and comparative chemical composition from selected in-use diesel and gasoline-fueled vehicles

Emission samples for toxicity testing and detailed chemical characterization were collected from a variety of gasoline- and diesel-fueled in-use vehicles operated on the Unified Driving Cycle on a chassis dynamometer. Gasoline vehicles included normal particle mass (particulate matter [PM]) emitters (tested at 72 and 30 degrees F), "black" and "white" smokers, and a new-technology vehicle (tested at 72 degrees F). Diesel vehicles included current-technology vehicles (tested at 72 and 30 degrees F) and a high PM emitter. Total PM emission rates ranged from below 3 mg/mi up to more than 700 mg/mi for the white smoker gasoline vehicle. Emission rates of organic and elemental carbon (OC/EC), elements (metals and associated analytes), ions, and a variety of particulate and semi-volatile organic compounds (polycyclic aromatic hydrocarbons [PAH], nitro-PAH, oxy-PAH, hopanes, and steranes) are reported for these vehicles. Speciated organic analysis also was conducted on the fuels and lube oils obtained from these vehicles after the emissions testing. The compositions of emissions were highly dependent on the fuel type (gasoline vs. diesel), the state of vehicle maintenance (low, average, or high emitters; white or black smokers), and ambient conditions (i.e., temperature) of the vehicles. Fuel and oil analyses from these vehicles showed that oil served as a repository for combustion byproducts (e.g., PAH), and oil-burning gasoline vehicles emitted PAH in higher concentrations than did other vehicles. These PAH emissions matched the PAH compositions observed in oil.     

PCDDs and PCDFs in vehicle exhaust particles in Japan.

Vehicle exhaust particles from gasoline and diesel engine cars were analyzed for PCDDs and PCDFs. The congener patterns of PCDDs and PCDFs in exhaust particles were different between gasoline and diesel engine cars. Suspended particulate matter from electrostatic precipitator connected to a highway tunnel was also analyzed for PCDDs and PCDFs. The congener pattern of suspended particular matter was different from both of gasoline and diesel engine cars. Total amounts of PCDDs/PCDFs sum concentrations in gasoline, diesel and suspended particulate matter were 0.21, 0.87 and 26.0 ng/g, respectively. The I-TEQs levels in gasoline, diesel and suspended particulate matter were 4.2, 11 and 242 pg/g, respectively.     

Occurrence and sources of particulate nitro-polycyclic aromatic hydrocarbons in ambient air in Denmark

The occurrence of selected nitro-polycyclic aromatic hydrocarbons (nitro-PAHs) associated with atmospheric particulate matter has been investigated at an urban site and at a semi-rural site. For this purpose an analysis method based on gas chromatography and tandem ion trap mass spectrometry has been developed and applied. The nitro-PAH levels have been compared with levels of other air pollutants including unsubstituted PAHs, inorganic gases and particulate matter, as well as with meteorological parameters. Correlations and concentration ratios suggest that the dominant source of 9-nitroanthracene at the urban site is direct emissions, whereas at the semirural site its dominant source is atmospheric formation. The atmospheric formation of 2-nitrofluoranthene and 2-nitropyrene generally seems to be initiated by OH radicals during the day rather than by NO₃ radicals at night. The average contribution of the OH initiated formation is estimated to be in the range of 90–100%. However, under wintertime conditions with cloudy weather implying low OH radical production, NO₃ radicals may also be important as initiators of nitro-PAH formation. Samples influenced by transport of polluted air masses from the European continent have significantly elevated concentrations of atmospherically formed nitro-PAHs. The directly emitted nitro-PAHs, 1-nitropyrene and 3-nitrofluoranthene, do not exhibit elevated levels during such long-range transport episodes.     

Determination of the toxic impurities 3,3′,4,4′-tetrachloroazobenzene and 3,3′,4,4′-tetrachloroazoxybenzent in commercial diuron, linuron and 3,4-dichloroaniline samples

Methods are described for the determination of 3,3′,4,4′-tetrachloroazobenzene (TCAB) and 3,3′,4,4′-tetrachloroazoxybenzene (TCAOB) in diuron and linuron formulations and in 3,4-dichloroaniline. The formulations were extracted with acetone, and after removal of solvent, the residue was partitioned between methanol-water and hexane. 3,4-Dichloroaniline products were partitioned between methanol-1M hydrochloric acid and hexane. The hexane extracts were purified by column chromatography on silica gel and analysed by gas chromatography with electron-capture detection. Detection limits for TCAB and TCAOB were around 0.1 ug/g using samples of one gram. Levels of 5.5 – 28 ug TCAB and 1.9 − < 0.05 ug TCAOB/g herbicide formulation and 2.4 – 460 ug TCAB/g TCAB/g 3,4-dichloroaniline have been found. TCAOB levels were below the detection limits in the 3,4-dichloroaniline samples. The presence of TCAB and TCAOB was confirmed by gas chromatography-mass spectrometry.     

Heavy Duty Diesel Particulate Emission Factors

For the past several years, EPA has been measuring particulate emissions from a variety of heavy-duty diesel engines through contracts with Southwest Research Institute. Particulate emissions samples have been collected using an exhaust splitter to divert a fraction of the engine exhaust into a standard dilution tunnel. A small fraction of the diluted exhaust from the tunnel is pulled through a filter from which particulate mass and, in some cases, organic content of the particulate is determined. This paper discusses the sampling system and gives particulate emission factors that have been computed from truck and bus fuel consumption data as well as average truck and bus speed data from New York and Los Angeles (freeway and nonfreeway usage). Average particulate emission test results (steady state tests) for 2-stroke engines were 4.74 g/kg fuel and for 4-stroke engines were 2.64 g/kg fuel. Using average particulate emissions results, a particulate emission factor range of 0.8 to 1.3 g/km was computed. Nationwide diesel particulate emissions were calculated to be 88,000 metric tons per year.     

Polycyclic aromatic hydrocarbon exhaust emissions from different reformulated diesel fuels and engine operating conditions

The study of light-duty diesel engine exhaust emissions is important due to their impact on atmospheric chemistry and air pollution. In this study, both the gas and the particulate phase of fuel exhaust were analyzed to investigate the effects of diesel reformulation and engine operating parameters. The research was focused on polycyclic aromatic hydrocarbon (PAH) compounds on particulate phase due to their high toxicity. These were analyzed using a gas chromatography–mass spectrometry (GC–MS) methodology.Although PAH profiles changed for diesel fuels with low-sulfur content and different percentages of aromatic hydrocarbons (5–25%), no significant differences for total PAH concentrations were detected. However, rape oil methyl ester biodiesel showed a greater number of PAH compounds, but in lower concentrations (close to 50%) than the reformulated diesel fuels. In addition, four engine operating conditions were evaluated, and the results showed that, during cold start, higher concentrations were observed for high molecular weight PAHs than during idling cycle and that the acceleration cycles provided higher concentrations than the steady-state conditions. Correlations between particulate PAHs and gas phase products were also observed.The emission of PAH compounds from the incomplete combustion of diesel fuel depended greatly on the source of the fuel and the driving patterns.     

Mutagenicity of Airborne Particulates Assessed by Salmonella Assay and the SOS Chromotest in Wrocław,Poland

Abstract

Ambient air particulate matter less than 2.5 μm in aerodynamic diameter (PM_2.5) samples were collected during summer and autumn using a Staplex high-volume air sampler. They were later extracted with dichloromethane in a Soxhlet apparatus. Polyaromatic hydrocarbon (PAH) content in extracts was determined by the high-performance liquid chromatography technique using fluorescence detection, whereas the nitro-PAH content was determined by gas chromatography using mass detection. Four Salmonella typhimurium strains (TA98, TA100, YG1041, and YG1042) were used in assays conducted with and without metabolic activation. The extracts were also tested with the SOS chromotest supplied by Environmental Biodetection Products Incorporated. The obtained results confirmed the Salmonella assay and the SOS chromotest usability for the purpose of atmospheric pollution monitoring within an urban agglomeration. The atmospheric pollution extracts under examination differed among each other regarding total content and percentage of individual compounds, depending on the season of sampling. The highest total PAH content and the highest nitro-PAH content in the tested samples as well as the most extensive range of detected compounds were found in the autumn season (heating season). The highest mutagenicity was noted for PM_2.5 samples collected in autumn. The high values of mutagenicity ratios and induction factors were obtained from assays carried out with and without metabolic activation, which is an argument for the presence of promutagens and direct mutagens. The YG1041 strain proved to be the most effective in detection of mutagenicity of the suspended dust extracts because of its notably high sensitivity to nitro-aromatic compounds. The SOS chromotest was very sensitive to a large spectrum of genotoxic air pollutants and showed a high degree of similarity with the results of the Salmonella assay. In comparison with the frequently used Ames test, the SOS chromotest enables quick analysis of the genotoxic effects of samples using only one tester strain. In addition, its miniaturized design decreases the consumption of tested samples.     

Factors Influencing the Emissions of Nitrated-Polynuclear Aromatic Hydrocarbons(Nitro-PAH) from Diesel Engines

The potential problem of 1-nitropyrene (1-NP) formation during filter sampling of diesel emissions from dilution tubes is assessed. Rates of formation are calculated using data generated from several independent filter exposure studies. A portion of the 1-NP (12% average) found in participates collected from light-duty (LDD) and heavy-duty diesels (HOD) was found to be due to formation on the filter under average sampling conditions of 10-15/1 dilution at 44°C with 3 ppm NO₂ for 23 min. On the average, the concentration of 1-NP in participates emitted from HDD is 16 times less than that found in LDD run under similiar transient conditions. The average emission rate of 1-NP generated from the LDD and HDD was 4.7 μg/km and 1.5 μg/km, respectively for the vehicles operating under Federal Test Procedure (FTP)-transient conditions. Under operating conditions which increase exhaust temperature (increased speed and load), the concentration of nitro-PAH is significantly reduced with a concurrent increase in the concentration of partially oxidized nitro-PAH and dinitro-PAH. The concentration of 1-NP in the particulates measured from HDD in these dilution tube studies (0.33-0.95 ppm, depending upon engine load) is comparable to that measured in highway tunnel experiments (0.54 ppm average).     

Idle Emissions from Medium Heavy-Duty Diesel and Gasoline Trucks

Abstract

Idle emissions data from 19 medium heavy-duty diesel and gasoline trucks are presented in this paper. Emissions from these trucks were characterized using full-flow exhaust dilution as part of the Coordinating Research Council (CRC) Project E-55/59. Idle emissions data were not available from dedicated measurements, but were extracted from the continuous emissions data on the low-speed transient mode of the medium heavy-duty truck (MHDTLO) cycle. The four gasoline trucks produced very low oxides of nitrogen (NO_x) and negligible particulate matter (PM) during idle. However, carbon monoxide (CO) and hydrocarbons (HCs) from these four trucks were approximately 285 and 153 g/hr on average, respectively. The gasoline trucks consumed substantially more fuel at an hourly rate (0.84 gal/hr) than their diesel counterparts (0.44 gal/hr) during idling. The diesel trucks, on the other hand, emitted higher NO_x (79 g/hr) and comparatively higher PM (4.1 g/hr), on average, than the gasoline trucks (3.8 g/hr of NO_x and 0.9 g/hr of PM, on average). Idle NO_x emissions from diesel trucks were high for post-1992 model year engines, but no trends were observed for fuel consumption. Idle emissions and fuel consumption from the medium heavy-duty diesel trucks (MHDDTs) were marginally lower than those from the heavy heavy-duty diesel trucks (HHDDTs), previously reported in the literature.     

An investigation of interurban variations in the chemical composition and mutagenic activity of airborne particulate organic matter using an integrated chemical class/bioassay system

Previous investigations in this laboratory have demonstrated that the mutagenic activities of extractable particulate organic matter (EOM) from cities which differ in their principal fuels and meteorology can vary significantly. To gain a better understanding of these interurban variations, an Integrated Chemical Class/Biological Screening System was developed and used for a more detailed examination of differences in the chemical composition and mutagenic activity of EOM. The screening system involved coupling in situ Ames mutagenicity determinations on high performance thin layer chromatography (HPTLC) plates with class specific chemical analyses on a second set of plates. The system was used to screen for mutagenic activity and selected chemical classes (including PAH, nitro-PAH, phenols, carboxylic acids, carbonyls, aza-arenes and alkylating agents) in EOM from the following sites: New York City; Elizabeth, N.J.; Mexico City; Beijing, China; Philadelphia, PA; and the Caldecott Tunnel (CA).The results of this study demonstrated mutagenic activity and chemical compositional differences in HPTLC subfractions of particulate organic matter from these cities and from the Caldecott Tunnel. The greatest interurban differences in chemical classes were observed for the phenols, carbonyl compounds and alkylating agents. Interurban variations in mutagenic activities were greatest for EOM subfractions of intermediate polarity. These differences are probably related to interurban differences in the fuels used, types of sources and atmospheric conditions. The relationships between these variables are not well understood at present.     

Levels of 3,3′,4,4′-tetrachloroazobenzene in herbicides and bulk reagents

The contamination levels of different commercial herbicides and bulk reagents with the carcinogen 3,3′,4,4′-tetrachloroazobenzene (TCAB) were determined by high resolution mass spectrometry. The concentrations vary from 0.00071 to 2.8 ug/g (ppm) for the herbicides and from 0.085 to 14 ug/g for the bulk reagents. They are thus lower than those of other reports.     

Contribution to bacterial mutagenicity from nitro-pah compounds in ambient aerosols

To demonstrate a method for the identification of mutagenic components in organic fractions of ambient aerosols, the mutagenic activity was studied in samples collected simultaneously for six consecutive days during the summer of 1931 at an urban site and a suburban site in southeast Michigan. The filter samples were extracted with dichloromethane and fractionated by thin layer chromatography (TLC) into sixteen fractions. The individual TLC fractions were then examined by the Ames test using tester strains TA98, TA98NR and TA98DNP₆. Similar daily variations in the activity and the mutagenicity profiles of the TLC fractions occurred at both sites. In samples collected from both locations, approximately half of the mutagenic activity was found in the four most polar fractions of the particulate extracts. The remaining mutagenic activity was distributed among the less polar fractions where PAH, nitro-PAH and dinitro-PAH would be eluted. The mutagenic activity in all fractions decreased sharply when tested with two nitroreductase deficient tester strains, TA98NR and TA98DNP₆, indicating that the mutagens (especially those in the polar fractions) were nitro-substituted polycyclic aromatic hydrocarbon compounds. Three nitro compounds, 1-nitropyrene, 1,6-dinitropyrene and 1,8-dinitropyrene were detected by high performance liquid chromatography (HPLC) but could account for no more than 3% of the total airborne mutagenicity. A National Bureau of Standards' Ambient Particulate Sample (SRM No. 1649), collected for a long sampling period of 18 months, differed markedly from the urban and suburban Michigan samples in its mutagenicity profile.     

Relative importance of school bus-related microenvironments to children's pollutant exposure

Real-time concentrations of black carbon, particle-bound polycyclic aromatic hydrocarbons, nitrogen dioxide, and fine particulate counts, as well as integrated and real-time fine particulate matter (PM2.5) mass concentrations were measured inside school buses during long commutes on Los Angeles Unified School District bus routes, at bus stops along the routes, at the bus loading/unloading zone in front of the selected school, and at nearby urban "background" sites. Across all of the pollutants, mean concentrations during bus commutes were higher than in any other microenvironment. Mean exposures (mean concentration times time spent in a particular microenvironment) in bus commutes were between 50 and 200 times greater than those for the loading/unloading microenvironment, and 20-40 times higher than those for the bus stops, depending on the pollutant. Although the analyzed school bus commutes represented only 10% of a child's day, on average they contributed one-third of a child's 24-hr overall black carbon exposure during a school day. For species closely related to vehicle exhaust, the within- cabin exposures were generally dominated by the effect of surrounding traffic when windows were open and by the bus's own exhaust when windows were closed. Low-emitting buses generally exhibited high concentrations only when traveling behind a diesel vehicle, whereas high-emitting buses exhibited high concentrations both when following other diesel vehicles and when idling without another diesel vehicle in front of the bus. To reduce school bus commute exposures, we recommend minimizing commute times, avoiding caravanning with other school buses, using the cleanest buses for the longest bus routes, maintaining conventional diesel buses to eliminate visible emissions, and transitioning to cleaner fuels and advanced particulate control technologies as soon as possible.     

Relative Importance of School Bus-Related Microenvironments to Children’s Pollutant Exposure

Abstract

Real‐time concentrations of black carbon, particle‐bound polycyclic aromatic hydrocarbons, nitrogen dioxide, and fine particulate counts, as well as integrated and real‐time fine particulate matter (PM_2.5) mass concentrations were measured inside school buses during long commutes on Los Angeles Unified School District bus routes, at bus stops along the routes, at the bus loading/unloading zone in front of the selected school, and at nearby urban “background” sites. Across all of the pollutants, mean concentrations during bus commutes were higher than in any other microenvironment. Mean exposures (mean concentration times time spent in a particular microenvironment) in bus commutes were between 50 and 200 times greater than those for the loading/unloading microenvironment, and 20–40 times higher than those for the bus stops, depending on the pollutant. Although the analyzed school bus commutes represented only 10% of a child’s day, on average they contributed one‐third of a child’s 24‐hr overall black carbon exposure during a school day. For species closely related to vehicle exhaust, the within‐cabin exposures were generally dominated by the effect of surrounding traffic when windows were open and by the bus’s own exhaust when windows were closed. Low‐emitting buses generally exhibited high concentrations only when traveling behind a diesel vehicle, whereas high‐emitting buses exhibited high concentrations both when following other diesel vehicles and when idling without another diesel vehicle in front of the bus. To reduce school bus commute exposures, we recommend minimizing commute times, avoiding caravanning with other school buses, using the cleanest buses for the longest bus routes, maintaining conventional diesel buses to eliminate visible emissions, and transitioning to cleaner fuels and advanced particulate control technologies as soon as possible.     

Characteristics of trans,trans-2,4-decadienal and polycyclic aromatic hydrocarbons in exhaust of diesel engine fueled with biodiesel

The use of biodiesel fuel as a substitute for fossil fuel in diesel engines has received increasing attention in recent years. This study is the first to investigate and compare the characteristics of mutagenic species, trans,trans-2,4-decadienal (tt-DDE), and polycyclic aromatic hydrocarbons (PAHs) in the diluted exhaust of diesel engines operated with diesel and biodiesel blend fuels. An engine of current design was operated on a dynamometer consistent with the US federal test procedure transient-cycle specifications. Petroleum diesel and a blend of petroleum diesel and biodiesel (B20) were tested. Exhaust sampling was carried out on diluted exhaust in a dilution tunnel with a constant-volume sampling system. Concentrations of tt-DDE and PAHs were analyzed by GC/MS. Although average PAH emission factors decreased from 1403 to 1051 μg bhp-h⁻¹, the results show that tt-DDE is evidently generated (1.28 μg bhp-h⁻¹) in the exhaust of diesel engine using B20 as fuel. This finding suggests that tt-DDE emission from the use of biodiesel should be taken into account in characterization and health-risk assessment. The results also show that tt-DDE is depleted in the diesel engine combustion process and the existence of tt-DDE in biodiesel is the major source of tt-DDE emission. The distribution of tt-DDE in the particulate phase is 55.3% under this study's sampling conditions. For diesel and B20, PAH phase distributions have similar trends. Lower molecular weight PAHs predominate in gaseous phase for both diesel and B20. Cold-start driving has higher tt-DDE and PAH emission factors, as well as a higher percentage of tt-DDE in particulate phase, than for warm-start driving.     

Mixed-model statistical analysis of fuel, equipment, mileage, and driving schedule effects on particulate matter emissions from heavy diesel-powered vehicles

An extensive experimental program has been conducted to evaluate the comparative effects of California Air Resources Board diesel fuel and an ultra-low-sulfur (S) diesel (with and without aftermarket passive filtering devices) on mass emissions of particulate matter (PM) in heavy vehicles. Tests have been performed on 20 Class 8 trucks at two high-mileage levels using two different driving schedules. The design of the test program facilitates the use of mixed-model statistical analysis, which allows more appropriate treatment of the explanatory variables than normally achieved. The analysis suggests that the ultra-low-S diesel fuel yields extremely low mean PM emissions when used in conjunction with a particulate filter, even at high mileage, but that the estimates are highly variable. The high degree of uncertainty, caused at least in part by large vehicle-to-vehicle variation, may obscure the true PM response and adversely impact attainment of increasingly more stringent diesel PM emissions standards in the United States.     

Chemical characterization and source identification of polycyclic aromatic hydrocarbons in aerosols originating from different sources

To obtain the characteristic factors or signatures of particulate polycyclic aromatic hydrocarbons (PAHs) to help identify the sources of particulate PAHs in the atmosphere, different carbonaceous aerosols were generated by burning different fossil fuels and biomass under different conditions in the laboratory, and the chemical characteristics of 14 PAHs were studied in detail. The results showed that (1) carbonaceous aerosols derived from domestic burning of coal, diesel fuel, and gasoline have much higher concentrations of PAHs than those derived from domestic burning of biomass; (2) carbonaceous aerosols derived from domestic burning of diesel fuel/gasoline have similar PAH components as those derived from high-temperature combustion of diesel fuel/gasoline, although the former have much higher concentrations of PAHs than the latter, suggesting that the burning temperature obviously affects the emitting amount of particulate PAHs, but only slightly influences the PAHs components; and (3) the ratios of benzo[b]fluoranthene/acenaphthylene, benzo[b]fluoranthene/fluorene, dibenzo[a,h]anthracene/acenaphthylene, dibenzo[a,h]anthracene/fluorine, and benzo[b]fluoranthene/benzo[k]fluoranthene in carbonaceous aerosols are sensitively dependent on their sources, indicating that these ratios are suitable for use as characteristic factors or signatures of particulate PAHs in the atmosphere.