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 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 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 A new diagnostic for tropospheric ozone production

2017 ◽  
Author(s):  
Peter M. Edwards ◽  
Mathew J. Evans
Keyword(s):  
Air Quality ◽  
Tropospheric Ozone ◽  
Transport Model ◽  
Chemical Transport ◽  
Ozone Production ◽  
Chemical Transport Model ◽  
Organic Species ◽  
Earth’S Climate ◽  
Oxidation Of Organics

Abstract. Tropospheric ozone is important for the Earth’s climate and air quality. It is produced during the oxidation of organics in the presence of nitrogen oxides. Due to the range of organic species emitted and the chain like nature of their oxidation, this chemistry is complex and understanding the role of different processes (emission, deposition, chemistry) is difficult. We demonstrate a new methodology for diagnosing ozone production based on the processing of bonds contained within emitted molecules, the fate of which is determined by the conservation of spin of the bonding electrons. Using this methodology to diagnose ozone production in the GEOS-Chem chemical transport model, we demonstrate its advantages over the standard diagnostic. We show that the number of bonds emitted, their chemistry and lifetime, and feedbacks on OH are all important in determining the ozone production within the model and its sensitivity to changes. This insight may allow future model-model comparisons to better identify the root causes of model differences.

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