scholarly journals Alkyl nitrate production and persistence in the Mexico City Plume

2009 ◽  
Vol 9 (6) ◽  
pp. 23755-23790 ◽  
Author(s):  
A. E. Perring ◽  
T. H. Bertram ◽  
D. K. Farmer ◽  
P. J. Wooldridge ◽  
J. Dibb ◽  
...  
Keyword(s):  
Mexico City ◽  
Near Field ◽  
Ozone Production ◽  
Gulf Region ◽  
Radical Chain ◽  
Major Pathway ◽  
Alkyl Nitrate ◽  
Peroxy Nitrates ◽  
Biogenic Compounds ◽  
City Plume

Abstract. Alkyl and multifunctional nitrates (ΣANs) have been observed to be a significant fraction of NOy in a number of different chemical regimes. Their formation is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. ΣANs also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Numerous studies have investigated the role of nitrate formation from biogenic compounds. Less attention has been paid to the role ΣANs may play in the complex mixtures of hydrocarbons typical of urban settings. Measurements of ΣANs, NO2, total peroxy nitrates (ΣPNs), HNO3 and a wide suite of hydrocarbons were obtained from the NASA DC-8 aircraft during spring of 2006 in and around Mexico City and the Gulf of Mexico. ΣANs were observed to be 10–20% of NOy in the Mexico City plume and to increase in importance with increased photochemical age. We describe three conclusions: 1) Correlations of ΣANs with odd-oxygen (Ox) indicate a stronger role for ΣANs in the photochemistry of Mexico City than is expected based on currently accepted photochemical mechanisms, 2) ΣAN formation suppresses peak ozone production rates by as much as 30% in the near-field of Mexico City and 3) ΣANs play a comparable role to ΣPNs in the export of NOy to the Gulf Region.

scholarly journals The production and persistence of ΣRONO<sub>2</sub> in the Mexico City plume

2010 ◽  
Vol 10 (15) ◽  
pp. 7215-7229 ◽  
Author(s):  
A. E. Perring ◽  
T. H. Bertram ◽  
D. K. Farmer ◽  
P. J. Wooldridge ◽  
J. Dibb ◽  
...  
Keyword(s):  
Mexico City ◽  
Near Field ◽  
Ozone Production ◽  
Gulf Region ◽  
Radical Chain ◽  
Major Pathway ◽  
Peroxy Nitrates ◽  
Biogenic Compounds ◽  
City Plume

Abstract. Alkyl and multifunctional nitrates (RONO2, ΣANs) have been observed to be a significant fraction of NOy in a number of different chemical regimes. Their formation is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. ΣANs also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Numerous studies have investigated the role of nitrate formation from biogenic compounds and in the remote atmosphere. Less attention has been paid to the role ΣANs may play in the complex mixtures of hydrocarbons typical of urban settings. Measurements of total alkyl and multifunctional nitrates, NO2, total peroxy nitrates (ΣPNs), HNO3 and a representative suite of hydrocarbons were obtained from the NASA DC-8 aircraft during spring of 2006 in and around Mexico City and the Gulf of Mexico. ΣANs were observed to be 10–20% of NOy in the Mexico City plume and to increase in importance with increased photochemical age. We describe three conclusions: (1) Correlations of ΣANs with odd-oxygen (Ox) indicate a stronger role for ΣANs in the photochemistry of Mexico City than is expected based on currently accepted photochemical mechanisms, (2) ΣAN formation suppresses peak ozone production rates by as much as 40% in the near-field of Mexico City and (3) ΣANs play a significant role in the export of NOy from Mexico City to the Gulf Region.

scholarly journals Airborne observations of total RONO<sub>2</sub>: new constraints on the yield and lifetime of isoprene nitrates

2009 ◽  
Vol 9 (4) ◽  
pp. 1451-1463 ◽  
Author(s):  
A. E. Perring ◽  
T. H. Bertram ◽  
P. J. Wooldridge ◽  
A. Fried ◽  
B. G. Heikes ◽  
...  
Keyword(s):  
Land Surface ◽  
Organic Nitrate ◽  
Radical Chain ◽  
Major Pathway ◽  
Wide Range ◽  
Peroxy Nitrates ◽  
The Us ◽  
Isoprene Nitrates ◽  
Isoprene Oxidation ◽  
The Individual

Abstract. Formation of isoprene nitrates (INs) is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Isoprene nitrates also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Current assessments indicate that formation rates of isoprene nitrates are uncertain to a factor of 2–3 and the subsequent fate of isoprene nitrates remains largely unconstrained by laboratory, field or modeling studies. Measurements of total alkyl and multifunctional nitrates (ΣANs), NO2, total peroxy nitrates (ΣPNs), HNO3, CH2O, isoprene and other VOC were obtained from the NASA DC-8 aircraft during summer 2004 over the continental US during the INTEX-NA campaign. These observations represent the first characterization of ΣANs over a wide range of land surface types and in the lower free troposphere. ΣANs were a significant, 12–20%, fraction of NOy throughout the experimental domain and ΣANs were more abundant when isoprene was high. We use the observed hydrocarbon species to calculate the relative contributions of ΣAN precursors to their production. These calculations indicate that isoprene represents at least three quarters of the ΣAN source in the summertime continental boundary layer of the US. An observed correlation between ΣANs and CH2O is used to place constraints on nitrate yields from isoprene oxidation, atmospheric lifetimes of the resulting nitrates and recycling efficiencies of nitrates during subsequent oxidation. We find reasonable fits to the data using sets of production rates, lifetimes and recycling efficiencies of INs as follows (4.4%, 16 h, 97%), (8%, 2.5 h, 79%) and (12%, 95 min, 67%). The analysis indicates that the lifetime of ΣANs as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates to reaction with OH, implying that the organic nitrate functionality is at least partially maintained through a second oxidation cycle.

scholarly journals Airborne observations of total RONO<sub>2</sub>: new constraints on the yield and lifetime of isoprene nitrates

2008 ◽  
Vol 8 (3) ◽  
pp. 12313-12341 ◽  
Author(s):  
A. E. Perring ◽  
T. H. Bertram ◽  
P. J. Wooldridge ◽  
A. Fried ◽  
B. G. Heikes ◽  
...  
Keyword(s):  
Land Surface ◽  
Organic Nitrate ◽  
Radical Chain ◽  
Major Pathway ◽  
Wide Range ◽  
Peroxy Nitrates ◽  
The Us ◽  
Isoprene Nitrates ◽  
Isoprene Oxidation ◽  
The Individual

Abstract. Formation of isoprene nitrates (INs) is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Isoprene nitrates also represent a large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Current assessments indicate that formation rates of isoprene nitrates are uncertain to a factor of 2–3 and the subsequent fate of isoprene nitrates remains largely unconstrained by laboratory, field or modeling studies. Measurements of total alkyl and multifunction nitrates (ΣANs), NO2, total peroxy nitrates (ΣPNs), HNO3, H2CO, isoprene and other VOC were obtained from the NASA DC-8 aircraft during summer 2004 over the continental US during the INTEX-NA campaign. These observations represent the first characterization of ΣANs over a wide range of land surface types and in the free troposphere. ΣANs were a significant, 12–20%, fraction of NOy throughout the experimental domain and ΣANs were more abundant when isoprene was high. We use the observed VOC to calculate the relative contributions of ΣAN precursors to their production. These calculations indicate that isoprene represents at least 76% of the ΣAN source in the summertime continental boundary layer of the US. An observed correlation between ΣANs and CH2O is used to place constraints on nitrate yields from isoprene oxidation, atmospheric lifetimes of the resulting nitrates and recycling efficiencies of nitrates during subsequent oxidation. We recommend sets of production rates, lifetimes and recycling efficiencies of INs as follows [4.4%, 5 h, 92%], [8%, 2.5 h, 84%] and [12%, 90 min, 74%]. The analysis indicates that the lifetime of ΣANs as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates to reaction with OH, implying that the organic nitrate functionality is at least partially maintained through a second oxidation cycle.

scholarly journals Assessing the regional impacts of Mexico City emissions on air quality and chemistry

2009 ◽  
Vol 9 (11) ◽  
pp. 3731-3743 ◽  
Author(s):  
M. Mena-Carrasco ◽  
G. R. Carmichael ◽  
J. E. Campbell ◽  
D. Zimmerman ◽  
Y. Tang ◽  
...  
Keyword(s):  
Air Quality ◽  
Mexico City ◽  
Ozone Production ◽  
Anthropogenic Aerosol ◽  
Near Surface ◽  
Mixing Ratios ◽  
Regional Impacts ◽  
Photolysis Rates ◽  
Regional Air Quality ◽  
The Impact

Abstract. The impact of Mexico City (MCMA) emissions is examined by studying its effects on air quality, photochemistry, and on ozone production regimes by combining model products and aircraft observations from the MILAGRO experiment during March 2006. The modeled influence of MCMA emissions to enhancements in surface level NOx, CO, and O3 concentrations (10–30% increase) are confined to distances <200 km, near surface. However, the extent of the influence is significantly larger at higher altitudes. Broader MCMA impacts (some 900 km Northeast of the city) are shown for specific outflow conditions in which enhanced ozone, NOy, and MTBE mixing ratios over the Gulf of Mexico are linked to MCMA by source tagged tracers and sensitivity runs. This study shows that the "footprint" of MCMA on average is fairly local, with exception to reactive nitrogen, which can be transported long range in the form of PAN, acting as a reservoir and source of NOx with important regional ozone formation implications. The simulated effect of MCMA emissions of anthropogenic aerosol on photochemistry showed a maximum regional decrease of 40% in J[NO2→NO+O], and resulting in the reduction of ozone production by 5–10%. Observed ozone production efficiencies are evaluated as a function of distance from MCMA, and by modeled influence from MCMA. These tend to be much lower closer to MCMA, or in those points where modeled contribution from MCMA is large. This research shows that MCMA emissions do effect on regional air quality and photochemistry, both contributing large amounts of ozone and its precursors, but with caveat that aerosol concentrations hinder formation of ozone to its potential due to its reduction in photolysis rates.

scholarly journals Comparison of Ozone Production Regimes between Two Mexican Cities: Guadalajara and Mexico City

Atmosphere ◽  
2016 ◽  
Vol 7 (7) ◽  
pp. 91 ◽  
Author(s):  
Isao Kanda ◽  
Roberto Basaldud ◽  
Miguel Magaña ◽  
Armando Retama ◽  
Ryushi Kubo ◽  
...  
Keyword(s):  
Mexico City ◽  
Ozone Production

scholarly journals Atmospheric oxidation in the Mexico City Metropolitan Area (MCMA) during April 2003

2006 ◽  
Vol 6 (9) ◽  
pp. 2753-2765 ◽  
Author(s):  
T. R. Shirley ◽  
W. H. Brune ◽  
X. Ren ◽  
J. Mao ◽  
R. Lesher ◽  
...  
Keyword(s):  
Steady State ◽  
Developing Country ◽  
Mexico City ◽  
Metropolitan Area ◽  
Urban Studies ◽  
Ozone Production ◽  
Atmospheric Oxidation ◽  
European Cities

Abstract. The Mexico City Metropolitan Area (MCMA) study in April 2003 had measurements of many atmospheric constituents, including OH and HO2. It provided the first opportunity to examine atmospheric oxidation in a megacity in a developing country that has more pollution than typical U.S. and European cities. At midday, OH typically reached 0.35 pptv (~7×106 cm−3), comparable to amounts observed in U.S. cities, but HO2 reached 40 pptv, more than observed in most U.S. cities. The OH reactivity was also measured, even during the highly polluted morning rush hour. MCMA's OH reactivity was 25 s−1 during most of the day and 120 s−1 at morning rush hour, which was several times greater than has been measured in any U.S. city. Median measured and modeled OH and HO2 agreed to within combined uncertainties, although for OH, the model exceeded the measurement by more than 30% during midday. OH production and loss, which were calculated from measurements, were in balance to within uncertainties, although production exceeded loss during morning rush hour. This imbalance has been observed in other cities. The HO2/OH ratio from measurements and steady-state analyses have essentially the same dependence on NO, except when NO was near 100 ppbv. This agreement is unlike other urban studies, in which HO2/OH ratio decreased much less than expected as NO increased. As a result of the active photochemistry in MCMA 2003, the median calculated ozone production from measured HO2 reached 50 ppb h−1, a much higher rate than observed in U.S. cities.

scholarly journals Oxidative capacity of the Mexico City atmosphere – Part 1: A radical source perspective

2010 ◽  
Vol 10 (14) ◽  
pp. 6969-6991 ◽  
Author(s):  
R. Volkamer ◽  
P. Sheehy ◽  
L. T. Molina ◽  
M. J. Molina
Keyword(s):  
Mexico City ◽  
Oxidative Capacity ◽  
Chemical Mechanism ◽  
Oh Radicals ◽  
Small Contribution ◽  
Radical Chain ◽  
Chain Reactions ◽  
Time Profiles ◽  
Concentration Time ◽  
Radical Production

Abstract. A detailed analysis of OH, HO2 and RO2 radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA). During spring of 2003 (MCMA-2003 field campaign) an extensive set of measurements was collected to quantify time-resolved ROx (sum of OH, HO2, RO2) radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1) was constrained by measurements of (1) concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO), formaldehyde (HCHO), ozone (O3), glyoxal (CHOCHO), and other oxygenated volatile organic compounds (OVOCs); (2) respective photolysis-frequencies (J-values); (3) concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated) and oxidants, i.e., OH- and NO3 radicals, O3; and (4) NO, NO2, meteorological and other parameters. The ROx production rate was calculated directly from these observations; the MCM was used to estimate further ROx production from unconstrained sources, and express overall ROx production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO2 and HO2 radicals into OH radicals). Daytime radical production is found to be about 10–25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: Oxygenated VOC other than HCHO about 33%; HCHO and O3 photolysis each about 20%; O3/alkene reactions and HONO photolysis each about 12%, other sources <3%. Nitryl chloride photolysis could potentially contribute ~15% additional radicals, while NO2* + water makes – if any – a very small contribution (~2%). The peak radical production of ~7.5 107 molec cm−3 s−1 is found already at 10:00 a.m., i.e., more than 2.5 h before solar noon. O3/alkene reactions are indirectly responsible for ~33% of these radicals. Our measurements and analysis comprise a database that enables testing of the representation of radical sources and radical chain reactions in photochemical models. Since the photochemical processing of pollutants in the MCMA is radical limited, our analysis identifies the drivers for ozone and SOA formation. We conclude that reductions in VOC emissions provide an efficient opportunity to reduce peak concentrations of these secondary pollutants, because (1) about 70% of radical production is linked to VOC precursors; (2) lowering the VOC/NOx ratio has the further benefit of reducing the radical re-cycling efficiency from radical chain reactions (chemical amplification of radical sources); (3) a positive feedback is identified: lowering the rate of radical production from organic precursors also reduces that from inorganic precursors, like ozone, as pollution export from the MCMA caps the amount of ozone that accumulates at a lower rate inside the MCMA. Continued VOC reductions will in the future result in decreasing peak concentrations of ozone and SOA in the MCMA.

scholarly journals Impact of model resolution on chemical ozone formation in Mexico City: application of the WRF-Chem model

2010 ◽  
Vol 10 (18) ◽  
pp. 8983-8995 ◽  
Author(s):  
X. Tie ◽  
G. Brasseur ◽  
Z. Ying
Keyword(s):  
Mexico City ◽  
Urban Areas ◽  
Air Pollutants ◽  
Emission Inventory ◽  
Meteorological Conditions ◽  
Transport Processes ◽  
Ozone Production ◽  
Model Resolution ◽  
Coarse Resolution ◽  
Photochemical Ozone

Abstract. The resolution of regional chemical/dynamical models has important effects on the calculation of the distributions of air pollutants in urban areas. In this study, the sensitivity of air pollutants and photochemical ozone production to different model resolutions is assessed by applying a regional chemical/dynamical model (version 3 of Weather Research and Forecasting Chemical model – WRF-Chemv3) to the case of Mexico City. The model results with 3, 6, 12, and 24 km resolutions are compared to local surface measurements of CO, NOx, and O3. The study shows that the model resolutions of 3 and 6 km provide reasonable simulations of surface CO, NOx, and O3 concentrations and of diurnal variations. The model tends to underestimate the measurements when the resolution is reduced to 12 km or less. The calculated surface CO, NOx, and O3 concentrations at 24 km resolution are significantly lower than measured values. This study suggests that the ratio of the city size to the threshold resolution is 6 to 1, and that this ratio can be considered as a test value in other urban areas for model resolution setting. There are three major factors related to the effects of model resolution on the calculations of O3 and O3 precursors, including; (1) the calculated meteorological conditions, (2) the spatial distribution for the emissions of ozone precursors, and (3) the non-linearity in the photochemical ozone production. Model studies suggest that, for the calculations of O3 and O3 precursors, spatial resolutions (resulting from different meteorological condition and transport processes) have larger impacts than the effect of the resolution associated with emission inventories. The model shows that, with coarse resolution of emission inventory (24 km) and high resolution for meteorological conditions (6 km), the calculated CO and O3 are considerably improved compared to the results obtained with coarse resolution for both emission inventory and meteorological conditions (24 km). The resolution of the surface emissions has important effects on the calculated concentration fields, but the effects are smaller than those resulting from the model resolution. This study also suggests that the effect of model resolution on O3 precursors leads to important impacts on the photochemical formation of ozone. This results directly from the non-linear relationship between O3 formation and O3 precursor concentrations. Finally, this study suggests that, considering the balance between model performance and required computation time on current computers, the 6 km resolution is an optimal resolution for the calculation of ozone and its precursors in urban areas like Mexico City.

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 Distribution, magnitudes, reactivities, ratios and diurnal patterns of volatile organic compounds in the Valley of Mexico during the MCMA 2002 and 2003 field campaigns

2006 ◽  
Vol 6 (4) ◽  
pp. 7563-7621 ◽  
Author(s):  
E. Velasco ◽  
B. Lamb ◽  
H. Westberg ◽  
E. Allwine ◽  
G. Sosa ◽  
...  
Keyword(s):  
Mexico City ◽  
Analytical Techniques ◽  
Ozone Production ◽  
Halogenated Hydrocarbons ◽  
Vehicle Exhaust ◽  
Rural Landscapes ◽  
Diurnal Patterns ◽  
Wide Range ◽  
Volatile Organic ◽  
Field Campaigns

Abstract. A wide array of volatile organic compound (VOC) measurements was conducted in the Valley of Mexico during the MCMA-2002 and 2003 field campaigns. Study sites included locations in the urban core, in a heavily industrial area and at boundary sites in rural landscapes. In addition, a novel mobile-laboratory-based conditional sampling method was used to collect samples dominated by fresh on-road vehicle exhaust to identify those VOCs whose ambient concentrations were primarily due to vehicle emissions. Five distinct analytical techniques were used: whole air canister samples with Gas Chromatography/Flame Ionization Detection (GC-FID), on-line chemical ionization using a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous real-time detection of olefins using a Fast Olefin Sensor (FOS), and long path measurements using UV Differential Optical Absorption Spectrometers (DOAS). The simultaneous use of these techniques provided a wide range of individual VOC measurements with different spatial and temporal scales. The VOC data were analyzed to understand concentration and spatial distributions, diurnal patterns, origin and reactivity in the atmosphere of Mexico City. The VOC burden (in ppbC) was dominated by alkanes (60%), followed by aromatics (15%) and olefins (5%). The remaining 20% was a mix of alkynes, halogenated hydrocarbons, oxygenated species (esters, ethers, etc.) and other unidentified VOCs. However, in terms of ozone production, olefins were the most relevant hydrocarbons. Elevated levels of toxic hydrocarbons, such as 1,3-butadiene, benzene, toluene and xylenes were also observed. Results from these various analytical techniques showed that vehicle exhaust is the main source of VOCs in Mexico City and that diurnal patterns depend on vehicular traffic. Finally, examination of the VOC data in terms of lumped modeling VOC classes and its comparison to the VOC lumped emissions reported in other photochemical air quality modeling studies suggests that some, but not all, VOC classes are underestimated in the emissions inventory by factors of 1.1 to 3.

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