Contributions of natural emissions to ozone and PM2.5 as simulated by the Community Multiscale Air Quality (CMAQ) model

The relative roles of natural and anthropogenic sources in determining ozone and fine particle concentrations over the continental United States (U.S.) are investigated using an expanded emissions inventory of natural sources and an updated version of the Community Multiscale Air Quality (CMAQ) model. Various 12-month CMAQ simulations for the year 2002 using different sets of input emissions data are combined to delineate the contributions of background pollutants (i.e., model boundary conditions), natural emissions, anthropogenic emissions, as well as the specific impacts of lightning and wildfires. Results are compared with observations and previous air quality model simulations. Wildfires and lightning are both identified as contributing significantly to ozone levels with lightning NO(x) adding as much as 25-30 ppbV (or up to about 50%) to surface 8-h average natural O(3) mixing ratios in the southeastern U.S. Simulated wildfire emissions added more than 50 ppbV (in some cases >90%) to 8-h natural O(3) at several locations in the west. Modeling also indicates that natural emissions (including biogenic, oceanic, geogenic and fires) contributed ≤ 40% to the annual average of total simulated fine particle mass over the eastern two-thirds of the U.S. and >40% across most of the western U.S. Biogenic emissions are the dominant source of particulate mass over the entire U.S. and wildfire emissions are secondary. Averaged over the entire modeling domain, background and natural ozone are dominant with anthropogenically derived ozone contributing up to a third of the total only during summer. Background contributions to fine particle levels are relatively insignificant in comparison. Model results are also contrasted with the U.S. Environmental Protection Agency (EPA) default values for natural light scattering particle concentrations to be used for regional haze regulatory decision-making. Regional differences in EPA guidance are not supported by the modeling and EPA uncertainty estimates for default values are far smaller than the modeled variability in natural particle concentrations.     

Mobile source and livestock feed contributions to regional ozone formation in Central California

A three-dimensional air quality model with 8 km horizontal resolution was applied to estimate the summertime ozone (O(3)) production from mobile sources and fermented livestock feed in California's San Joaquin Valley (SJV) during years 2000, 2005, 2010, 2015, and 2020. Previous studies have estimated that animal feed emissions of volatile organic compounds (VOCs) have greater O(3) formation potential than mobile-source VOC emissions when averaging across the entire SJV. The higher spatial resolution in the current study shows that the proximity of oxides of nitrogen (NO(x)) and VOC emissions from mobile sources enhances their O(3) formation potential. Livestock feed VOC emissions contributed 3-4 ppb of peak O(3) (8-h average) in Tulare County and 1-2 ppb throughout the remainder of the SJV during the CCOS 2000 July-August episode. In total, livestock feed contributed ~3.5 tons of the ground level peak O(3) (8 h average) in the SJV region, and mobile VOC contributed ~12 tons in this episode. O(3) production from mobile sources is declining over time in response to emissions control plans that call for cleaner fuels and engines with advanced emissions controls. Projecting forward to the year 2020, mobile-source VOC emissions are predicted to produce ~3 tons of the ground level peak O(3)(8-h average) and livestock feed VOC emissions are predicted to contribute ~2.5 tons making these sources nearly equivalent.     

Regional air quality: local and interstate impacts of NO(x) and SO2 emissions on ozone and fine particulate matter in the eastern United States

While the U.S. air quality management system is largely designed and managed on a state level, many critical air quality problems are now recognized as regional. In particular, concentrations of two secondary pollutants, ozone and particulate matter, are often above regulated levels and can be dependent on emissions from upwind states. Here, impacts of statewide emissions on concentrations of local and downwind states' ozone and fine particulate matter are simulated for three seasonal periods in the eastern United States using a regional Eulerian photochemical model. Impacts of ground level NO(x) (e.g., mobile and area sources), elevated NO(x) (e.g., power plants and large industrial sources), and SO2 emissions are examined. An average of 77% of each state's ozone and PM(2.5) concentrations that are sensitive to the emissions evaluated here are found to be caused by emissions from other states. Delaware, Maryland, New Jersey, Virginia, Kentucky, and West Virginia are shown to have high concentrations of ozone and PM(2.5) caused by interstate emissions. When weighted by population, New York receives increased interstate contributions to these pollutants and contributions to ozone from local emissions are generally higher. When accounting for emission rates, combined states from the western side of the modeling domain and individual states such as Illinois, Tennessee, Indiana, Kentucky, and Georgia are major contributors to interstate ozone. Ohio, Indiana, Tennessee, Kentucky, and Illinois are the major contributors to interstate PM(2.5). When accounting for an equivalent mass of emissions, Tennessee, Kentucky, West Virginia, Virginia, and Alabama contribute large fractions of these pollutants to other states.     

Propagation of uncertainty in hourly utility NOx emissions through a photochemical grid air quality model: a case study for the Charlotte, NC, modeling domain

One of the major hypothesized sources of uncertainties in air quality model inputs is the emission inventory. A probabilistic hourly NOx emission inventory for 32 units of nine coal-fired power plants in the Charlotte domain for the year 1995 was propagated through the Multiscale Air Quality Simulation Platform (MAQSIP). The inventory was developed using time series techniques. Time series for a 4-d episode were simulated and propagated through the air quality model 50 times in order to represent the ranges of uncertainty in hourly emissions and predicted ozone levels. Intra-unit autocorrelation in emissions and inter-unit dependence were accounted for. The range of uncertainty in predicted ozone was greater when inter-unit dependence was included as compared to when units were treated as statistically independent. Uncertainties in maximum ozone hourly or 8-h concentrations at a specific location could be attributed to a specific power plant based upon regression analysis. Out of 3969 grid cells in the modeling domain, there were 43 and 1654 grid cells with a probability greater than 0.9 of exceeding a 1-h 120 ppb standard and an 8-h 80 ppb standard, respectively. The time series of predicted ozone values had similar autocorrelation as compared to monitored data. The implications of these results for air quality management are addressed.     

Nonlinear response of ozone to emissions: source apportionment and sensitivity analysis

For secondary air pollutants, precursor emissions may impact concentrations in nonlinear and interdependent manners. We explore the nonlinear responses of one such pollutant, ozone, to emissions of its precursors, nitrogen oxides (NOx) and volatile organic compounds. Modeling is conducted for a high ozone episode in the southeastern United States, applying a second-order direct sensitivity method in a regional air quality model. As applied here, the sensitivity method neglects most aerosol and aqueous chemistry processes. Inclusion of second-order sensitivities is shown to enable accurate characterization of response to large perturbations in emissions. An index is introduced to characterize the nonlinearity of ozone response to NOx emitted from each source region. Nonlinearity is found to increase with the tonnage and emission density of the source region. Interactions among the impacts of emission sources are shown to lead to discrepancies between source contribution attributed to an ensemble of emitters and the sum of the contributions attributed to each component. A method is introduced for applying these "cross-sensitivity" interactions to assess the uncertainty of sensitivity and source apportionment estimates arising from uncertainty in an emissions inventory. For ozone response to NOx, underestimates in emission rates lead to underprediction of total source contribution but overprediction of per-ton sensitivity.     

Emission and atmospheric transport of particulate PAHs in Northeast Asia

The emission, concentration levels, and transboundary transport of particulate polycyclic aromatic hydrocarbons (PAHs) in Northeast Asia were investigated using particulate PAH measurements, the newly developed emission inventory (Regional Emission inventory in ASia for Persistent Organic Pollutants version, REAS-POP), and the chemical transport model (Regional Air Quality Model ver2 for POPs version, RAQM2-POP). The simulated concentrations of the nine particulate PAHs agreed well with the measured concentrations, and the results firmly established the efficacy of REAS/RAQM2-POP. It was found that the PAH concentrations in Beijing (China, source region), which were emitted predominantly from domestic coal, domestic biofuel, and other transformations of coal (including coke production), were approximately 2 orders of magnitude greater than those monitored at Noto (Japan, leeward region). In Noto, the PAH concentrations showed seasonal variations; the PAH concentrations were high from winter to spring due to contributions from domestic coal, domestic biofuel, and other transformations of coal, and low in summer. In summer, these contribution were decrease, instead, other sources, such as the on-road mobile source, were relatively increased compared with those in winter. These seasonal variations were due to seasonal variations in emissions from China, as well as transboundary transport across the Asian continent associated with meteorological conditions.     

Source apportionment of PM2.5 at an urban IMPROVE site in Seattle, Washington

The multivariate receptor models Positive Matrix Factorization (PMF) and Unmix were used along with the EPA's Chemical Mass Balance model to deduce the sources of PM2.5 at a centrally located urban site in Seattle, WA. A total of 289 filter samples were obtained with an IMPROVE sampler from 1996 through 1999 and were analyzed for 31 particulate elements including temperature-resolved fractions of the particulate organic and elemental carbon. All three receptor models predicted that the major sources of PM2.5 were vegetative burning (including wood stoves), mobile sources, and secondary particle formation with lesser contributions from resuspended soil and sea spray. The PMF and Unmix models were able to resolve a fuel oil combustion source as well as distinguish between diesel emissions and other mobile sources. In addition, the average source contribution estimates via PMF and Unmix agreed well with an existing emissions inventory. Using the temperature-resolved organic and elemental carbon fractions provided in the IMPROVE protocol, rather than the total organic and elemental carbon, allowed the Unmix model to separate diesel from other mobile sources. The PMF model was able to do this without the additional carbon species, relying on selected trace elements to distinguish the various combustion sources.     

Anthropogenic atmospheric emissions of antimony and its spatial distribution characteristics in China

An integrated inventory of atmospheric antimony (Sb) emissions from anthropogenic activities in China is compiled for the years 2005-2009. Emissions are estimated for all major anthropogenic sources for the first time. We estimate that the national emissions of antimony are 818 metric tons (t) in 2009, with the largest contribution from coal combustion at 61.8% of the total, while 26.7% of Sb is emitted from nonferrous metals smelting. Emissions are heaviest in Guizhou province, mainly due to small-scale combustion of high-Sb coal without emission control devices, and in Hunan province, where extensive smelting occurs. Furthermore, Sb emissions from 2188 large point sources and area sources are distributed within latitude/longitude-based grids with a resolution of 30 min × 30 min where Sb emissions are largely concentrated in highly populated and industrialized southwestern China, the east central region, and coastal areas. The uncertainties in our bottom-up inventory are quantified as -11% to 40% by Monte Carlo simulation. We recommend continuous field testing of coal combustors and smelters in China to improve the accuracy of these estimates.     

Diagnostic model evaluation for carbonaceous PM2.5 using organic markers measured in the southeastern U.S

Summertime concentrations of fine particulate carbon in the southeastern United States are consistently underestimated by air quality models. In an effort to understand the cause of this error, the Community Multiscale Air Quality model is instrumented to track primary organic and elemental carbon contributions from fifteen different source categories. The model results are speciated using published source profiles and compared with ambient measurements of 100 organic markers collected at eight sites in the Southeast during the 1999 summer. Results indicate that modeled contributions from vehicle exhaust and biomass combustion, the two largest sources of carbon in the emission inventory, are unbiased across the region. In Atlanta, good model performance for total carbon (TC) is attributed to compensating errors: overestimation of vehicle emissions with underestimations of other sources. In Birmingham, 35% of the TC underestimation can be explained by deficiencies in primary sources. Cigarette smoke and vegetative detritus are not in the inventory, but contribute less than 3% of the TC at each site. After the model results are adjusted for source-specific errors using the organic-marker measurements, an average of 1.6 microgC m(-3) remain unexplained. This corresponds to 26-38% of ambient TC concentrations at urban sites and up to 56% at rural sites. The most likely sources of unexplained carbon are discussed.     

Hydrochloric acid: an overlooked driver of environmental change

Research on the ecosystem impacts of acidifying pollutants, and measures to control them, has focused almost exclusively on sulfur (S) and nitrogen (N) compounds. Hydrochloric acid (HCl), although emitted by coal burning, has been overlooked as a driver of ecosystem change because most of it was considered to redeposit close to emission sources rather than in remote natural ecosystems. Despite receiving little regulatory attention, measures to reduce S emissions, and changes in energy supply, have led to a 95% reduction in United Kingdom HCl emissions within 20 years. Long-term precipitation, surface water, and soil solution data suggest that the near-disappearance of HCl from deposition could account for 30-40% of chemical recovery from acidification during this time, affecting both near-source and remote areas. Because HCl is highly mobile in reducing environments, it is a more potent acidifier of wetlands than S or N, and HCl may have been the major driver of past peatland acidification. Reduced HCl loadings could therefore have affected the peatland carbon cycle, contributing to increases in dissolved organic carbon leaching to surface waters. With many regions increasingly reliant on coal for power generation, HCl should be recognized as a potentially significant constituent of resulting emissions, with distinctive ecosystem impacts.     

Adjoint sensitivity analysis of ozone nonattainment over the continental United States

An application of the adjoint method in air quality management is demonstrated. We use a continental scale chemical transport model (STEM) to calculate the sensitivities of a nationwide U.S. ozone national ambient air quality standard (NAAQS) nonattainment metric to precursor emissions for the period July 1 to August 15, 2004. The model shows low bias and error (-4 and 24%, respectively), particularly for areas with high ozone concentrations. The nonattainment metric accounts for both 1-h and 8-h ozone standards, but is dominated by the 8-h exceedances (97% of the combined metric). Largest values of sensitivities are found to be with respect to emissions in the south and southeast U.S., Ohio River Valley, and California. When nonattainment sensitivities are integrated over the entire U.S., NOx emissions account for the largest contribution (62% of the total), followed by biogenic and anthropogenic VOCs (24% and 14%, respectively). For NOx emissions, point/area and mobile sources account for 54% and 46% of the total sensitivities, respectively. We also provide a state-by-state comparison for the nonattainment magnitude, nonattainment sensitivity, and emission magnitudes to explore the influence of interstate transport of ozone and its precursors, and policy implications of the results. Our analysis of the nationwide ozone nonattainment metric suggests that simple cap-and-trade programs may prove inadequate in achieving sought-after air quality objectives.     

Regional modeling of the atmospheric fate and transport of benzene and diesel particles

The Community Multiscale Air Quality model (CMAQ) was modified to simulate the atmospheric fate and transport of benzene and diesel particles. We simulated the July 11-15, 1995 period over a domain covering the eastern United States with a 12-km horizontal resolution and a finer (4 km) resolution over a part of the northeastern United States that includes Washington, DC and New York City. The meteorological fields were obtained from a simulation conducted earlier with the mesoscale model MM5. Gridded emission files for benzene and diesel particles were developed using the SMOKE modeling system. The results of the model simulations showed that benzene concentrations were commensurate with available measurements. Over the 4-km resolution domain, a comparison between simulated and measured 24-h average concentrations showed a fractional error of 0.46, a fractional bias of 0.14, and a coefficient of determination (r2) of 0.25. A comparison between simulated benzene hourly concentrations in New York City and in the Brigantine Wilderness Area, NJ, showed that urban concentrations were greater than the remote area concentrations by a factor of 2-5. The results of the diesel particle simulations showed spatial and temporal patterns that were similar to those obtained for benzene. However, because of the lesser contribution of on-road mobile sources to diesel particle emissions compared to benzene emissions, diesel particle concentrations showed stronger gradients between urban areas and remote areas. A comparison between diesel particle concentrations in New York City and in the Brigantine Wilderness Area, NJ, showed that the urban concentrations were greater than the remote area concentrations by a factor of 2-10. Assuming that diesel particles consist of 50% "elemental" carbon (EC), the simulated EC concentrations were in close agreement (within 10%) with the measured concentration in the urban area (Washington, DC) but were significantly lower than the measured EC concentrations in the remote area (Brigantine Wilderness Area). This result suggests that other sources beside diesel fuel engines contribute to atmospheric EC concentrations and that EC may not be a good surrogate for diesel particles. A comparison of both benzene and diesel particle simulated concentrations between an urban area (New York City) and a remote area (Brigantine Wilderness Area) shows that, at a spatial resolution of 4 km, the regional background may contribute from 10 to 20% to the peak concentrations. These results suggest that the regional background may not be negligible and should be taken into account in urban air toxics studies.     

Photochemical modeling of emissions trading of highly reactive volatile organic compounds in Houston, Texas. 2. Incorporation of chlorine emissions

As part of the State Implementation Plan for attaining the National Ambient Air Quality Standard for ozone, the Texas Commission of Environmental Quality has created a Highly Reactive Volatile Organic Compounds (HRVOC) Emissions Cap and Trade Program for industrial point sources in the Houston/Galveston/Brazoria area. This series of papers examines the potential air quality impacts of this new emission trading program through photochemical modeling of potential trading scenarios; this paper examines the air quality impact of allowing facilities to trade chlorine emission reductions for HRVOC allocations on a reactivity weighted basis. The simulations indicate that trading of anthropogenic chlorine emission reductions for HRVOC allowances at a single facility or between facilities, in general, resulted in improvements in air quality. Decreases in peak 1-h averaged and 8-h averaged ozone concentrations associated with trading chlorine emissions for HRVOC allocations on a Maximum Incremental Reactivity (MIR) basis were up to 0.74 ppb (0.63%) and 0.56 ppb (0.61%), respectively. Air quality metrics based on population exposure decreased by up to 3.3% and 4.1% for 1-h and 8-h averaged concentrations. These changes are small compared to the maximum changes in ozone concentrations due to the VOC emissions from these sources (5-10 ppb for 8-h averages; up to 30 ppb for 1-h averages) and the chlorine emissions from the sources (5-10 ppb for maximum concentrations over wide areas and up to 70 ppb in localized areas). The simulations indicate that the inclusion of chlorine emissions in the trading program is likely to be beneficial to air quality and is unlikely to cause localized increases in ozone concentrations ("hot spots").     

Factors influencing mobile source particulate matter emissions-to-exposure relationships in the Boston urban area

Benefit-cost and regulatory impact analyses often use atmospheric dispersion models with coarse resolution to estimate the benefits of proposed mobile source emission control regulations. This approach may bias health estimates or miss important intra-urban variability for primary air pollutants. In this study, we estimate primary fine particulate matter (PM2.5) intake fractions (iF; the fraction of a pollutant emitted from a source that is inhaled by the population) for each of 23 398 road segments in the Boston Metro Core area to evaluate the potential for intra-urban variability in the emissions-to-exposure relationship. We estimate iFs using the CAL3QHCR line source model combined with residential populations within 5000 m of each road segment. The annual average values for the road segments range from 0.8 to 53 per million, with a mean of 12 per million. On average, 46% of the total exposure is realized within 200 m of the road segment, though this varies from 0 to 93% largely due to variable population patterns. Our findings indicate the likelihood of substantial intra-urban variability in mobile source primary PM2.5 iF that accounting for population movement with time, localized meteorological conditions, and street-canyon configurations would likely increase.     

Dispersion modeling of polycyclic aromatic hydrocarbons from combustion of biomass and fossil fuels and production of coke in Tianjin, China

A USEPA, procedure, ISCLT3 (Industrial Source Complex Long-Term), was applied to model the spatial distribution of polycyclic aromatic hydrocarbons (PAHs) emitted from various sources including coal, petroleum, natural gas, and biomass into the atmosphere of Tianjin, China. Benzo[a]pyrene equivalent concentrations (BaPeq) were calculated for risk assessment. Model results were provisionally validated for concentrations and profiles based on the observed data at two monitoring stations. The dominant emission sources in the area were domestic coal combustion, coke production, and biomass burning. Mainly because of the difference in the emission heights, the contributions of various sources to the average concentrations at receptors differ from proportions emitted. The shares of domestic coal increased from approximately 43% at the sources to 56% at the receptors, while the contributions of coking industry decreased from approximately 23% at the sources to 7% at the receptors. The spatial distributions of gaseous and particulate PAHs were similar, with higher concentrations occurring within urban districts because of domestic coal combustion. With relatively smaller contributions, the other minor sources had limited influences on the overall spatial distribution. The calculated average BaPeq value in air was 2.54 +/- 2.87 ng/m3 on an annual basis. Although only 2.3% of the area in Tianjin exceeded the national standard of 10 ng/m3, 41% of the entire population lives within this area.     

Mercury emissions from biomass burning in China

Biomass burning covers open fires (forest and grassland fires, crop residue burning in fields, etc.) and biofuel combustion (crop residues and wood, etc., used as fuel). As a large agricultural country, China may produce large quantities of mercury emissions from biomass burning. A new mercury emission inventory in China is needed because previous studies reflected outdated biomass burning with coarse resolution. Moreover, these studies often adopted the emission factors (mass of emitted species per mass of biomass burned) measured in North America. In this study, the mercury emissions from biomass burning in China (excluding small islands in the South China Sea) were estimated, using recently measured mercury concentrations in various biomes in China as emission factors. Emissions from crop residues and fuelwood were estimated based on annual reports distributed by provincial government. Emissions from forest and grassland fires were calculated by combining moderate resolution imaging spectroradiometer (MODIS) burned area product with combustion efficiency (ratio of fuel consumption to total available fuels) considering fuel moisture. The average annual emission from biomass burning was 27 (range from 15.1 to 39.9) Mg/year. This inventory has high spatial resolution (1 km) and covers a long period (2000-2007), making it useful for air quality modeling.     

Atmospheric chlorine chemistry in southeast Texas: impacts on ozone formation and control

Recent evidence has demonstrated that chlorine radical chemistry can enhance tropospheric hydrocarbon oxidation and has the potential to enhance ozone formation in urban atmospheres. To assess these effects quantitatively, an August-September 2000 photochemical episode in southeast Texas was simulated using the comprehensive air quality model, with extensions (CAMx). During this episode, ambient measurements of a unique marker of atmospheric chlorine chemistry, 1-chloro-3-methyl-3butene-2-one (CMBO), were made and model performance was assessed by comparing modeled and observed CMBO mixing ratios. The model predicted ambient CMBO mixing ratios within the uncertainty limits associated with the emissions inventory, so the model was used to assess the impacts of chlorine chemistry on ozone formation. Based on the current emissions inventory, chlorine emissions have the potential to enhance 1-h-averaged ozone mixing ratios by 70 ppb, in very localized areas, during morning hours. Over wider areas, and at times of day when peak ozone concentrations are observed, the impacts of chlorine emissions on ozone concentrations are typically less than 10 ppb. Chlorine emissions also influenced changes in ozone concentrations due to hydrocarbon and NOx emission controls.     

Impact of finer grid resolution on the spatial distribution of vehicle emissions inventories

The ability to model air quality dispersion at increasingly smaller resolutions requires a concomitant improvement in the resolution of the gridded mobile source emissions used as input to these models. Two methods are currently used to allocate mobile emissions to grids; because of the limitations associated with these methods, their application is usually restricted to coarser grid resolutions. This paper uses a new mobile emissions inventory model (UCDrive) to explore the spatial distribution of mobile source emissions using finer grid cell resolutions. Our results indicate that the new model improves the precision of the spatial allocation of mobile source emissions, which in turn improves our ability to identify and implement pollutant control strategies.     

Modeling the atmospheric transport and deposition of PCDD/F to the Great Lakes

Atmospheric deposition is a significant loading pathway for polychlorinated dibenzo-p-dioxins and dibenzofurans (dioxin) to the Great Lakes. An innovative approach using NOAA's HYSPLIT atmospheric fate and transport model was developed to estimate the 1996 dioxin contribution to each lake from each of 5,700 point sources and 42,600 area sources in a U.S./Canadian air emissions inventory. These unusually detailed source-receptor modeling results show that deposition to each lake arises from a broad geographical region, with significant contributions from up to 2,000 km away. The source categories contributing most significantly to 1996 dioxin deposition appear to be municipal waste incineration, iron sintering, medical waste incineration, and cement kilns burning hazardous waste. Model-predicted air concentrations and deposition fluxes were consistent with ambient measurement data, within the uncertainties in each, but there may be a moderate tendency toward underestimation using midrange emissions estimates. The most likely reason for this tendency appears to be missing or underestimated emissions sources, but in-situ atmospheric formation of octachlorinated dibenzo-p-dioxin (OCDD) and heptachlorinated dibenzo-p-dioxin (HpCDD) may have also contributed. Despite uncertainties, the findings regarding the relative importance of different sources types and source regions appear to be relatively robust and may be useful in prioritizing pollution prevention efforts.     

Vehicle traffic as a source of particulate polycyclic aromatic hydrocarbon exposure in the Mexico City metropolitan area

Surface properties of aerosols in the Mexico City metropolitan area have been measured in a variety of exposure scenarios related to vehicle emissions in 2002, using continuous, real-time instruments. The objective of these experiments is to describe ambient and occupational particulate polycyclic aromatic hydrocarbon (PAH) concentrations associated with vehicular traffic and facilities using diesel vehicles. Median total particulate PAH concentrations along Mexico City's roadways range from 60 to 910 ng m(-3), averaged over a minimum of 1 h. These levels are approximately 5 times higher than concentrations measured in the United States and among the highest measured ambient values reported in the literature. The ratio of particulate PAH concentration to aerosol active surface area is much higher along roadways and in other areas of fresh vehicle emissions, compared to ratios measured at sites influenced more by aged emissions or noncombustion sources. For particles freshly emitted by vehicles, PAH and elemental carbon (EC) concentrations are correlated because they both originate during the combustion process. Comparison of PAH versus EC and active surface area concentrations at different locations suggests that surface PAH concentrations may diminish with particle aging. These results indicate that exposure to vehicle-related PAH emissions on Mexico City's roadways may present an important public health risk.