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Browsing by Author "Molina, L. T."

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    Application of positive matrix factorization to on-road measurements for source apportionment of diesel- and gasoline-powered vehicle emissions in Mexico City
    Thornhill, D. A.; Williams, A. E.; Onasch, T. B.; Wood, E.; Herndon, S. C.; Kolb, C. E.; Knighton, W. B.; Zavala, M.; Molina, L. T.; Marr, Linsey C. (Copernicus Publications, 2010)
    The goal of this research is to quantify diesel- and gasoline-powered motor vehicle emissions within the Mexico City Metropolitan Area (MCMA) using on-road measurements captured by a mobile laboratory combined with positive matrix factorization (PMF) receptor modeling. During the MCMA-2006 ground-based component of the MILAGRO field campaign, the Aerodyne Mobile Laboratory (AML) measured many gaseous and particulate pollutants, including carbon dioxide, carbon monoxide (CO), nitrogen oxides (NOx), benzene, toluene, alkylated aromatics, formaldehyde, acetaldehyde, acetone, ammonia, particle number, fine particulate mass (PM2.5), and black carbon (BC). These serve as inputs to the receptor model, which is able to resolve three factors corresponding to gasoline engine exhaust, diesel engine exhaust, and the urban background. Using the source profiles, we calculate fuel-based emission factors for each type of exhaust. The MCMA's gasoline-powered vehicles are considerably dirtier, on average, than those in the US with respect to CO and aldehydes. Its diesel-powered vehicles have similar emission factors of NOx and higher emission factors of aldehydes, particle number, and BC. In the fleet sampled during AML driving, gasoline-powered vehicles are found to be responsible for 97% of total vehicular emissions of CO, 22% of NOx, 95-97% of each aromatic species, 72-85% of each carbonyl species, 74% of ammonia, negligible amounts of particle number, 26% of PM2.5, and 2% of BC; diesel-powered vehicles account for the balance. Because the mobile lab spent 17% of its time waiting at stoplights, the results may overemphasize idling conditions, possibly resulting in an underestimate of NOx and overestimate of CO emissions. On the other hand, estimates of the inventory that do not correctly account for emissions during idling are likely to produce bias in the opposite direction.The resulting fuel-based estimates of emissions are lower than in the official inventory for CO and NOx and higher for VOCs. For NOx, the fuel-based estimates are lower for gasoline-powered vehicles but higher for diesel-powered ones compared to the official inventory. While conclusions regarding the inventory should be interpreted with care because of the small sample size, 3.5 h of driving, the discrepancies with the official inventory agree with those reported in other studies.
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    Evaluation of mobile emissions contributions to Mexico City's emissions inventory using on-road and cross-road emission measurements and ambient data
    Zavala, M.; Herndon, S. C.; Wood, E. C.; Onasch, T. B.; Knighton, W. B.; Marr, Linsey C.; Kolb, C. E.; Molina, L. T. (Copernicus Publications, 2009)
    Mobile emissions represent a significant fraction of the total anthropogenic emissions burden in the Mexico City Metropolitan Area (MCMA) and, therefore, it is crucial to use top-down techniques informed by on-road exhaust measurements to evaluate and improve traditional bottom-up official emissions inventory (EI) for the city. We present the measurements of on-road fleet-average emission factors obtained using the Aerodyne mobile laboratory in the MCMA in March 2006 as part of the MILAGRO/MCMA-2006 field campaign. A comparison of our on-road emission measurements with those obtained in 2003 using essentially the same measurement techniques and analysis methods indicates that, in the three year span, NO emission factors remain within the measured variability ranges whereas emission factors of aldehydes and aromatics species were reduced for all sampled driving conditions. We use a top-down fuel-based approach to evaluate the mobile emissions from the gasoline fleet estimated in the bottom-up official 2006 MCMA mobile sources. Within the range of measurement uncertainties, we found probable slight overpredictions of mean EI estimates on the order of 20-28% for CO and 14-20% for NO. However, we identify a probable EI discrepancy of VOC mobile emissions between 1.4 and 1.9; although estimated benzene and toluene mobile emissions in the inventory seem to be well within the uncertainties of the corresponding emissions estimates. Aldehydes mobile emissions in the inventory, however, seem to be underpredicted by factors of 3 for HCHO and 2 for CH(3)CHO. Our on-road measurement-based estimate of annual emissions of organic mass from PM(1) particles suggests a severe underprediction (larger than a factor of 4) of PM(2.5) mobile emissions in the inventory. Analyses of ambient CO, NO(x) and CO/NO(x) concentration trends in the MCMA indicate that the early morning ambient CO/NO(x) ratio has decreased at a rate of about 1.9 ppm/ppm/year over the last two decades due to reductions in CO levels rather than by NO(x). These trends, together with the analysis of fuel sales and fleet size, suggest that the relative contribution of diesel vehicles to overall NO(x) levels has increased over time in the city. Despite the impressive increase in the size of the vehicle fleet between 2000 and 2006, the early morning ambient concentrations of CO and NO(x) have not increased accordingly, probably due to the reported low removal rates of older vehicles, which do not have emissions control technologies, and partially due to the much lower emissions from newer gasoline vehicles. This indicates that an emission-based air quality improvement strategy targeting large reductions of emissions from mobile sources should be directed towards a significant increase of the removal rate of older, highly-polluting, vehicles.
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    Sources and transformations of particle-bound polycyclic aromatic hydrocarbons in Mexico City
    Marr, Linsey C.; Dzepina, K.; Jimenez, Jose L.; Reisen, F.; Bethel, H. L.; Arey, J.; Gaffney, J. S.; Marley, N. A.; Molina, L. T.; Molina, M. J. (Copernicus Publications, 2006-05-01)
    Understanding sources, concentrations, and transformations of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere is important because of their potent mutagenicity and carcinogenicity. The measurement of particle-bound PAHs by three different methods during the Mexico City Metropolitan Area field campaign in April 2003 presents a unique opportunity for characterization of these compounds and intercomparison of the methods. The three methods are ( 1) collection and analysis of bulk samples for time-integrated gas- and particle-phase speciation by gas chromatography/ mass spectrometry; ( 2) aerosol photoionization for fast detection of PAHs on particles' surfaces; and ( 3) aerosol mass spectrometry for fast analysis of size and chemical composition. This research represents the first time aerosol mass spectrometry has been used to measure ambient PAH concentrations and the first time that fast, real-time methods have been used to quantify PAHs alongside traditional filter-based measurements in an extended field campaign. Speciated PAH measurements suggest that motor vehicles and garbage and wood burning are important sources in Mexico City. The diurnal concentration patterns captured by aerosol photoionization and aerosol mass spectrometry are generally consistent. Ambient concentrations of particle-phase PAHs typically peak at similar to 110 ng m(-3) during the morning rush hour and rapidly decay due to changes in source activity patterns and dilution as the boundary layer rises, although surface-bound PAH concentrations decay faster. The more rapid decrease in surface versus bulk PAH concentrations during the late morning suggests that freshly emitted combustion-related particles are quickly coated by secondary aerosol material in Mexico City's atmosphere and may also be transformed by heterogeneous reactions.
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    Spatial and temporal variability of particulate polycyclic aromatic hydrocarbons in Mexico City
    Thornhill, D. A.; de Foy, B.; Herndon, S. C.; Onasch, T. B.; Wood, E. C.; Zavala, M.; Molina, L. T.; Gaffney, J. S.; Marley, N. A.; Marr, Linsey C. (Copernicus Publications, 2008)
    As part of the Megacities Initiative: Local and Global Research Observations (MILAGRO) study in the Mexico City Metropolitan Area in March 2006, we measured particulate polycyclic aromatic hydrocarbons (PAHs) and other gaseous species and particulate properties, including light absorbing carbon or effective black carbon (BC), at six locations throughout the city. The measurements were intended to support the following objectives: to describe spatial and temporal patterns in PAH concentrations, to gain insight into sources and transformations of PAHs and BC, and to quantify the relationships between PAHs and other pollutants. Total particulate PAHs at the Instituto Mexicano del Petroleo (T0 supersite) located near downtown averaged 50 ng m(-3), and aerosol active surface area averaged 80 mm(2) m(-3). PAHs were also measured on board the Aerodyne Mobile Laboratory, which visited six sites encompassing a mixture of different land uses and a range of ages of air parcels transported from the city core. A combination of analyses of time series, back trajectories, concentration fields, pollutant ratios, and correlation coefficients supports the concept of T0 as an urban source site, T1 as a receptor site with strong local sources, Pedregal and PEMEX as intermediate sites, Pico Tres Padres as a vertical receptor site, and Santa Ana as a downwind receptor site. Weak intersite correlations suggest that local sources are important and variable and that exposure to PAHs and BC cannot be represented by a single regional-scale value. The relationships between PAHs and other pollutants suggest that a variety of sources and ages of particles are present. Among carbon monoxide, nitrogen oxides (NO(x)), and carbon dioxide, particulate PAHs are most strongly correlated with NO(x). Mexico City's PAH/BC mass ratio of 0.01 is similar to that found on a freeway loop in the Los Angeles area and approximately 8-30 times higher than that found in other cities. Evidence also suggests that primary combustion particles are rapidly coated by secondary aerosol in Mexico City. If so, their optical properties may change, and the lifetime of PAHs may be prolonged if the coating protects them against photodegradation or heterogeneous reactions.
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    Vehicle fleet emissions of black carbon, polycyclic aromatic hydrocarbons, and other pollutants measured by a mobile laboratory in Mexico City
    Jiang, M.; Marr, Linsey C.; Dunlea, E. J.; Herndon, S. C.; Jayne, John T.; Kolb, C. E.; Knighton, W. B.; Rogers, T. M.; Zavala, M.; Molina, L. T.; Molina, M. J. (Copernicus Publications, 2005-12-01)
    Black carbon ( BC) and polycyclic aromatic hydrocarbons (PAHs) are of concern due to their effects on climate and health. The main goal of this research is to provide the first estimate of emissions of BC and particle-phase PAHs (PPAHs) from motor vehicles in Mexico City. The emissions of other pollutants including carbon monoxide ( CO), oxides of nitrogen (NOx), volatile organic compounds (VOCs), and particulate matter of diameter 2.5 mu m and less (PM2.5) are also estimated. As a part of the Mexico City Metropolitan Area field campaign in April 2003 (MCMA-2003), a mobile laboratory was driven throughout the city. The laboratory was equipped with a comprehensive suite of gas and particle analyzers, including an aethalometer that measured BC and a photoionization aerosol sensor that measured PPAHs. While driving through traffic, the mobile lab continuously sampled exhaust plumes from the vehicles around it. We have developed a method of automatically identifying exhaust plumes, which are then used as the basis for calculation of fleet-average emissions. In the approximately 75 h of on-road sampling during the field campaign, we have identified similar to 30 000 exhaust measurement points that represent a variety of vehicle types and driving conditions. The large sample provides a basis for estimating fleet-average emission factors and thus the emission inventory. Motor vehicles in the Mexico City area are estimated to emit 1700 +/- 200 metric tons BC, 57 +/- 6 tons PPAHs, 1 190 000 +/- 40 000 tons CO, 120 000 +/- 3000 tons NOx, 240 000 +/- 50 000 tons VOCs, and 4400 +/- 400 tons PM2.5 per year, not including cold start emissions. The estimates for CO, NOx, and PPAHs may be low by up to 10% due to the slower response time of analyzers used to measure these species. Compared to the government's official motor vehicle emission inventory for the year 2002, the estimates for CO, NOx, VOCs, and PM2.5 are 38% lower, 23% lower, 27% higher, and 25% higher, respectively. The distributions of emission factors of BC, PPAHs, and PM2.5 are highly skewed, i.e. asymmetric, while those for benzene, measured as a surrogate for total VOCs, and NOx are less skewed. As a result, the total emissions of BC, PPAHs, and PM2.5 could be reduced by approximately 50% if the highest 20% of data points were removed, but "super polluters" are less influential on overall NOx and VOC emissions.