scholarly journals Correlation of secondary organic aerosol with odd oxygen in Mexico City

2008 ◽  
Vol 35 (15) ◽  
Author(s):  
Scott C. Herndon ◽  
Timothy B. Onasch ◽  
Ezra C. Wood ◽  
Jesse H. Kroll ◽  
Manjula R. Canagaratna ◽  
...  
Keyword(s):  
Mexico City ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Odd Oxygen

scholarly journals Investigation of the correlation between odd oxygen and secondary organic aerosol in Mexico City and Houston

2010 ◽  
Vol 10 (2) ◽  
pp. 3547-3604 ◽  
Author(s):  
E. C. Wood ◽  
M. R. Canagaratna ◽  
S. C. Herndon ◽  
J. H. Kroll ◽  
T. B. Onasch ◽  
...  
Keyword(s):  
Mexico City ◽  
Secondary Organic Aerosol ◽  
Formation Rate ◽  
Organic Aerosol ◽  
Ozone Production ◽  
Volatile Components ◽  
Petrochemical Plant ◽  
Plant Emissions ◽  
Photochemical Aging ◽  
Odd Oxygen

Abstract. Many recent models underpredict secondary organic aerosol (SOA) particulate matter (PM) concentrations in polluted regions, indicating serious deficiencies in the models' chemical mechanisms and/or missing SOA precursors. Since tropospheric photochemical ozone production is much better understood, we investigate the correlation of odd-oxygen ([Ox]≡[O3]+[NO2]) and the oxygenated component of organic aerosol (OOA), which is interpreted as a surrogate for SOA. OOA and Ox measured in Mexico City in 2006 and Houston in 2000 were well correlated in air masses where both species were formed on similar timescales (less than 8 h) and not well correlated when their formation timescales or location differed greatly. When correlated, the ratio of these two species ranged from 30 μg m−3 ppm−1 (STP) in Houston during time periods affected by large petrochemical plant emissions to as high as 160 μg m−3 ppm−1 in Mexico City, where typical values were near 120 μg m−3 ppm−1. On several days in Mexico City, the [OOA]/[Ox] ratio decreased by a factor of ~2 between 08:00 and 13:00 LT. This decrease is only partially attributable to evaporation of the least oxidized and most volatile components of OOA; differences in the diurnal emission trends and timescales for photochemical processing of SOA precursors compared to ozone precursors also likely contribute to the observed decrease. The extent of OOA oxidation increased with photochemical aging. Calculations of the ratio of the SOA formation rate to the Ox production rate using ambient VOC measurements and traditional laboratory SOA yields are lower than the observed [OOA]/[Ox] ratios by factors of 5 to 15, consistent with several other models' underestimates of SOA. Calculations of this ratio using emission factors for organic compounds from gasoline and diesel exhaust do not reproduce the observed ratio. Although not succesful in reproducing the atmospheric observations presented, modeling P(SOA)/P(Ox) can serve as a useful test of photochemical models using improved formulation mechanisms for SOA.

scholarly journals Investigation of the correlation between odd oxygen and secondary organic aerosol in Mexico City and Houston

2010 ◽  
Vol 10 (18) ◽  
pp. 8947-8968 ◽  
Author(s):  
E. C. Wood ◽  
M. R. Canagaratna ◽  
S. C. Herndon ◽  
T. B. Onasch ◽  
C. E. Kolb ◽  
...  
Keyword(s):  
Mexico City ◽  
Secondary Organic Aerosol ◽  
Formation Rate ◽  
Organic Aerosol ◽  
Ozone Production ◽  
Volatile Components ◽  
Petrochemical Plant ◽  
Plant Emissions ◽  
Photochemical Aging ◽  
Odd Oxygen

Abstract. Many recent models underpredict secondary organic aerosol (SOA) particulate matter (PM) concentrations in polluted regions, indicating serious deficiencies in the models' chemical mechanisms and/or missing SOA precursors. Since tropospheric photochemical ozone production is much better understood, we investigate the correlation of odd-oxygen ([Ox]≡[O3]+[NO2]) and the oxygenated component of organic aerosol (OOA), which is interpreted as a surrogate for SOA. OOA and Ox measured in Mexico City in 2006 and Houston in 2000 were well correlated in air masses where both species were formed on similar timescales (less than 8 h) and not well correlated when their formation timescales or location differed greatly. When correlated, the ratio of these two species ranged from 30 μg m−3/ppm (STP) in Houston during time periods affected by large petrochemical plant emissions to as high as 160 μg m−3/ppm in Mexico City, where typical values were near 120 μg m−3/ppm. On several days in Mexico City, the [OOA]/[Ox] ratio decreased by a factor of ~2 between 08:00 and 13:00 local time. This decrease is only partially attributable to evaporation of the least oxidized and most volatile components of OOA; differences in the diurnal emission trends and timescales for photochemical processing of SOA precursors compared to ozone precursors also likely contribute to the observed decrease. The extent of OOA oxidation increased with photochemical aging. Calculations of the ratio of the SOA formation rate to the Ox production rate using ambient VOC measurements and traditional laboratory SOA yields are lower than the observed [OOA]/[Ox] ratios by factors of 5 to 15, consistent with several other models' underestimates of SOA. Calculations of this ratio using emission factors for organic compounds from gasoline and diesel exhaust do not reproduce the observed ratio. Although not succesful in reproducing the atmospheric observations presented, modeling P(SOA)/P(Ox) can serve as a useful test of photochemical models using improved formulation mechanisms for SOA.

scholarly journals Evaluation of the volatility basis-set approach for the simulation of organic aerosol formation in the Mexico City metropolitan area

2010 ◽  
Vol 10 (2) ◽  
pp. 525-546 ◽  
Author(s):  
A. P. Tsimpidi ◽  
V. A. Karydis ◽  
M. Zavala ◽  
W. Lei ◽  
L. Molina ◽  
...  
Keyword(s):  
Mexico City ◽  
Metropolitan Area ◽  
Secondary Organic Aerosol ◽  
Transport Model ◽  
Three Dimensional ◽  
Organic Aerosol ◽  
Basis Set ◽  
Aerosol Formation ◽  
Chemical Transport Model ◽  
Starting Point

Abstract. New primary and secondary organic aerosol modules have been added to PMCAMx, a three dimensional chemical transport model (CTM), for use with the SAPRC99 chemistry mechanism based on recent smog chamber studies. The new modelling framework is based on the volatility basis-set approach: both primary and secondary organic components are assumed to be semivolatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. This new framework with the use of the new volatility basis parameters for low-NOx and high-NOx conditions tends to predict 4–6 times higher anthropogenic SOA concentrations than those predicted with the older generation of models. The resulting PMCAMx-2008 was applied in Mexico City Metropolitan Area (MCMA) for approximately a week during April 2003 during a period of very low regional biomass burning impact. The emission inventory, which uses as a starting point the MCMA 2004 official inventory, is modified and the primary organic aerosol (POA) emissions are distributed by volatility based on dilution experiments. The predicted organic aerosol (OA) concentrations peak in the center of Mexico City, reaching values above 40 μg m−3. The model predictions are compared with the results of the Positive Matrix Factorization (PMF) analysis of the Aerosol Mass Spectrometry (AMS) observations. The model reproduces both Hydrocarbon-like Organic Aerosol (HOA) and Oxygenated Organic Aerosol (OOA) concentrations and diurnal profiles. The small OA underprediction during the rush-hour periods and overprediction in the afternoon suggest potential improvements to the description of fresh primary organic emissions and the formation of the oxygenated organic aerosols, respectively, although they may also be due to errors in the simulation of dispersion and vertical mixing. However, the AMS OOA data are not specific enough to prove that the model reproduces the organic aerosol observations for the right reasons. Other combinations of contributions of primary and secondary organic aerosol production rates may lead to similar results. The model results strongly suggest that, during the simulated period, transport of OA from outside the city was a significant contributor to the observed OA levels. Future simulations should use a larger domain in order to test whether the regional OA can be predicted with current SOA parameterizations. Sensitivity tests indicate that the predicted OA concentration is especially sensitive to the volatility distribution of the emissions in the lower volatility bins.

A missing sink for gas-phase glyoxal in Mexico City: Formation of secondary organic aerosol

2007 ◽  
Vol 34 (19) ◽  
Author(s):  
Rainer Volkamer ◽  
Federico San Martini ◽  
Luisa T. Molina ◽  
Dara Salcedo ◽  
Jose L. Jimenez ◽  
...  
Keyword(s):  
Gas Phase ◽  
Mexico City ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
City Formation

Insights into the nature of secondary organic aerosol in Mexico City during the MILAGRO experiment 2006

2010 ◽  
Vol 44 (3) ◽  
pp. 312-319 ◽  
Author(s):  
Elizabeth A. Stone ◽  
Curtis J. Hedman ◽  
Jiabin Zhou ◽  
Mark Mieritz ◽  
James J. Schauer
Keyword(s):  
Mexico City ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol

scholarly journals Spectro-microscopic measurements of carbonaceous aerosol aging in Central California

2013 ◽  
Vol 13 (4) ◽  
pp. 9179-9216
Author(s):  
R. C. Moffet ◽  
T. C. Rödel ◽  
S. T. Kelly ◽  
X. Y. Yu ◽  
G. T. Carroll ◽  
...  
Keyword(s):  
Organic Carbon ◽  
Mexico City ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Urban Site ◽  
Carbonaceous Aerosols ◽  
Data Set ◽  
Carbonaceous Particles ◽  
X Ray ◽  
Individual Particles

Abstract. Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES) was designed to study carbonaceous aerosols in the natural environment of Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of pollution accumulation event (27–29 June 2010), when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX) and scanning transmission X-ray microscopy coupled with near edge X-ray absorption spectroscopy (STXM/NEXAFS) were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm diameter) increased with plume age as did the organic mass per particle. Comparison of the CARES spectro-microscopic data set with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that individual particles in Mexico City contained twice as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (30%) was larger than at the CARES urban site (10%) and the most aged samples from CARES contained less carbon-carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed results provided by these spectro-microscopic measurements will allow for a comprehensive evaluation of aerosol process models used in climate research.

scholarly journals Evaluation of the volatility basis-set approach for the simulation of organic aerosol formation in the Mexico City metropolitan area

2009 ◽  
Vol 9 (3) ◽  
pp. 13693-13737 ◽  
Author(s):  
A. P. Tsimpidi ◽  
V. A. Karydis ◽  
M. Zavala ◽  
W. Lei ◽  
L. Molina ◽  
...  
Keyword(s):  
Mexico City ◽  
Metropolitan Area ◽  
Secondary Organic Aerosol ◽  
Transport Model ◽  
Organic Aerosol ◽  
Basis Set ◽  
Aerosol Formation ◽  
Chemical Transport Model ◽  
Modeling Framework ◽  
Starting Point

Abstract. New primary and secondary organic aerosol modules have been added to PMCAMx, a three dimensional chemical transport model (CTM), for use with the SAPRC99 chemistry mechanism based on recent smog chamber studies. The new modeling framework is based on the volatility basis-set approach: both primary and secondary organic components are assumed to be semivolatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. This new framework with the use of the new volatility basis parameters for low-NOx and high-NOx conditions tends to predict 4–6 times higher anthropogenic SOA concentrations than those predicted with older generation of models. The resulting PMCAMx-2008 was applied in Mexico City Metropolitan Area (MCMA) for approximately a week during April of 2003. The emission inventory, which uses as starting point the MCMA 2004 official inventory, is modified and the primary organic aerosol (POA) emissions are distributed by volatility based on dilution experiments. The predicted organic aerosol (OA) concentrations peak in the center of Mexico City reaching values above 40 μg m−3. The model predictions are compared with Aerosol Mass Spectrometry (AMS) observations and their Positive Matrix Factorization (PMF) analysis. The model reproduces both Hydrocarbon-like Organic Aerosol (HOA) and Oxygenated Organic Aerosol (OOA) concentrations and diurnal profiles. The small OA underprediction during the rush hour periods and overprediction in the afternoon suggest potential improvements to the description of fresh primary organic emissions and the formation of the oxygenated organic aerosols respectively, although they may also be due to errors in the simulation of dispersion and vertical mixing. However, the AMS OOA data are not specific enough to prove that the model reproduces the organic aerosol observations for the right reasons. Other combinations of contributions of primary, aged primary, and secondary organic aerosol production rates may lead to similar results. The model results suggest strongly that during the simulated period transport of OA from outside the city was a significant contributor to the observed OA levels. Future simulations should use a larger domain in order to test whether the regional OA can be predicted with current SOA parameterizations. Sensitivity tests indicate that the predicted OA concentration is especially sensitive to the volatility distribution of the emissions in the lower volatility bins.

scholarly journals Spectro-microscopic measurements of carbonaceous aerosol aging in Central California

2013 ◽  
Vol 13 (20) ◽  
pp. 10445-10459 ◽  
Author(s):  
R. C. Moffet ◽  
T. C. Rödel ◽  
S. T. Kelly ◽  
X. Y. Yu ◽  
G. T. Carroll ◽  
...  
Keyword(s):  
Organic Carbon ◽  
Mexico City ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Urban Site ◽  
Organic Carbon Content ◽  
Carbonaceous Aerosols ◽  
Carbonaceous Particles ◽  
X Ray ◽  
Individual Particles

Abstract. Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES) was designed to study carbonaceous aerosols in the natural environment of the Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of a pollution accumulation event (27–29 June 2010), when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer-controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX) and scanning transmission X-ray microscopy coupled with near-edge X-ray absorption spectroscopy (STXM/NEXAFS) were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm equivalent circular diameter) increased with plume age, as did the organic mass per particle. Comparison of the CARES spectro-microscopic dataset with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that fresh particles in Mexico City contained three times as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (ranging from 16.6 to 47.3%) was larger than at the CARES urban site (13.4–15.7%), and the most aged samples from CARES contained fewer carbon–carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed results provided by these spectro-microscopic measurements will allow for a comprehensive evaluation of aerosol process models used in climate research.

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