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1
Xu, Liting, Qilei Yang, Lihua Hu, Dong Wang, Yue Peng, Zheru Shao, Chunmei Lu, and Junhua Li. "Insights over Titanium Modified FeMgOx Catalysts for Selective Catalytic Reduction of NOx with NH3: Influence of Precursors and Crystalline Structures." Catalysts 9, no. 6 (June 24, 2019): 560. http://dx.doi.org/10.3390/catal9060560.
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Titanium modified FeMgOx catalysts with different precursors were prepared by coprecipitation method with microwave thermal treatment. The iron precursor is a key factor affecting the surface active component. The catalyst using FeSO4 and Mg(NO3)2 as precursors exhibited enhanced catalytic activity from 225 to 400 °C, with a maximum NOx conversion of 100%. Iron oxides existed as γ-Fe2O3 in this catalyst. They exhibited highly enriched surface active oxygen and surface acidity, which were favorable for low-temperature selective catalytic reduction (SCR) reaction. Besides, it showed advantage in surface area, spherical particle distribution and pores connectivity. Amorphous iron-magnesium-titanium mixed oxides were the main phase of the catalysts using Fe(NO3)3 as a precursor. This catalyst exhibited a narrow T90 of 200/250–350 °C. Side reactions occurred after 300 °C producing NOx, which reduced the NOx conversion. The strong acid sites inhibited the side reactions, and thus improved the catalytic performance above 300 °C. The weak acid sites appeared below 200 °C, and had a great impact on the low-temperature catalytic performance. Nevertheless, amorphous iron-magnesium-titanium mixed oxides blocked the absorption and activation between NH3 and the surface strong acid sites, which was strengthened on the γ-Fe2O3 surface.
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Morin, S., R. Sander, and J. Savarino. "Simulation of the diurnal variations of the oxygen isotope anomaly (Δ<sup>17</sup>O) of reactive atmospheric species." Atmospheric Chemistry and Physics Discussions 10, no. 12 (December 14, 2010): 30405–51. http://dx.doi.org/10.5194/acpd-10-30405-2010.
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Abstract. The isotope anomaly (Δ17O) of secondary atmospheric species such as nitrate (NO3−) or hydrogen peroxyde (H2O2) has potential to provide useful constrains on their formation pathways. Indeed, the Δ17O of their precursors (NOx, HOx etc.) differs and depends on their interactions with ozone, which is the main source of non-zero Δ17O in the atmosphere. Interpreting variations of Δ17O in secondary species requires an in-depth understanding of the Δ17O of their precursors taking into account non-linear chemical regimes operating under various environmental settings. We present results from numerical simulations carried out using the atmospheric chemistry box model (CAABA/MECCA) to explicitly compute the diurnal variations of the isotope anomaly of short-lived species such as NOx and HOx. Δ17O was propagated from ozone to other species (NO, NO2, OH, HO2, RO2, NO3, N2O5, HONO, HNO3, HNO4, H2O2) according to the classical mass-balance equation, through the implementation of various sets of hypotheses pertaining to the transfer of Δ17O during chemical reactions. The model confirms that diurnal variations in Δ17O of NOx are well predicted by the photochemical steady-state relationship during the day, but that at night a different approach must be employed (i.e. "fossilization" of the Δ17O of NOx as soon as the photolytical lifetime of NOx drops below ca. 5 min). We quantify the diurnally-integrated isotopic signature (DIIS) of sources of atmospheric nitrate and H2O2 under the various environmental conditions analyzed, which is of particular relevance to larger-scale implementations of Δ17O where high computational costs cannot be afforded.
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SINHA, PRIYANKA, Siddharth Singh, and POOJA SAROJ. "Relationship of Surface Ozone (O3) with its precursors and meteorological parameters over New Delhi, India." MAUSAM 73, no. 4 (September 30, 2022): 829–42. http://dx.doi.org/10.54302/mausam.v73i4.5510.
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In the present study, continuous measurements of Surface Ozone (O3), Oxides of Nitrogen (NOx (NO+ NO2)), and carbon monoxide (CO), monitored at five different locations in Delhi National Capital Region have been studied for the period 2013 – 2019. The five monitoring locations used are namely IMD Lodi Road, IGI Airport Palam, CV Raman Dheerpur, CRRI Mathura Road, and NCMRWF Noida. The average hourly concentration of O3, NO, NO2, CO, NOx (NO + NO2), and OX(NO2 +O3) are found in the range of 32.44 ppb to 36.57 ppb, 19.46 to 28.09 ppb, 20.83 to 26.89 ppb,1.67 to 1.89 ppm,43.04 to 54.99 ppb, and 54.06 to 60.99 ppb respectively during the study period. Diurnal variation of NOx and CO Concentrations show higher values during the morning (0600-0900h) and late evening (1900-2400h) hours while the highest concentrations of ozone have been observed during afternoon hours. The relationship between NO, NO2, and surface O3 as a function of NOx has also been examined during daylight hours (0500hrs IST to 1900 hrs IST) and chemical coupling of the three species i.e. NO, NO2 and O3 have been studied. The ground-level concentration of Ozone has been found to decrease with increasing NOx concentration during the daytime. The variations in concentrations of oxidants (NO2 + O3) with the concentration of [NOx] have been studied to examine the contributing pollution sources of oxidants at all the study sites. The average rate of change of O3 concentrations (dO3/dt) has been examined at all five locations. The monthly and diurnal variation of oxidants [OX] at all the study locations has shown a strong positive correlation with temperature whereas a negative correlation with humidity.
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Wang, Yujue, Min Hu, Yuchen Wang, Jing Zheng, Dongjie Shang, Yudong Yang, Ying Liu, et al. "The formation of nitro-aromatic compounds under high NO<sub><i>x</i></sub> and anthropogenic VOC conditions in urban Beijing, China." Atmospheric Chemistry and Physics 19, no. 11 (June 7, 2019): 7649–65. http://dx.doi.org/10.5194/acp-19-7649-2019.
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Abstract. Nitro-aromatic compounds (NACs), as important contributors to the light absorption by brown carbon, have been widely observed in various ambient atmospheres; however, their formation in the urban atmosphere was little studied. In this work, we report an intensive field study of NACs in summer 2016 at an urban Beijing site, characterized by both high-NOx and anthropogenic VOC dominated conditions. We investigated the factors that influence NAC formation (e.g., NO2, VOC precursors, RH and photolysis) through quantification of eight NACs, along with major components in fine particulate matter, selected volatile organic compounds, and gases. The average total concentration of the quantified NACs was 6.63 ng m−3, higher than those reported in other summertime studies (0.14–6.44 ng m−3). 4-Nitrophenol (4NP, 32.4 %) and 4-nitrocatechol (4NC, 28.5 %) were the top two most abundant NACs, followed by methyl-nitrocatechol (MNC), methyl-nitrophenol (MNP), and dimethyl-nitrophenol (DMNP). The oxidation of toluene and benzene in the presence of NOx was found to be a more dominant source of NACs than primary biomass burning emissions. The NO2 concentration level was found to be an important factor influencing the secondary formation of NACs. A transition from low- to high-NOx regimes coincided with a shift from organic- to inorganic-dominated oxidation products. The transition thresholds were NO2 ∼ 20 ppb for daytime and NO2∼25 ppb for nighttime conditions. Under low-NOx conditions, NACs increased with NO2, while the NO3- concentrations and (NO3-)/NACs ratios were lower, implying organic-dominated products. Under high-NOx conditions, NAC concentrations did not further increase with NO2, while the NO3- concentrations and (NO3-)/NACs ratios showed increasing trends, signaling a shift from organic- to inorganic-dominated products. Nighttime enhancements were observed for 3M4NC and 4M5NC, while daytime enhancements were noted for 4NP, 2M4NP, and DMNP, indicating different formation pathways for these two groups of NACs. Our analysis suggested that the aqueous-phase oxidation was likely the major formation pathway of 4M5NC and 3M5NC, while photo-oxidation of toluene and benzene in the presence of NO2 could be more important for the formation of nitrophenol and its derivatives. Using the (3M4NC+4M5NC) ∕ 4NP ratios as an indicator of the relative contribution of aqueous-phase and gas-phase oxidation pathways to NAC formation, we observed that the relative contribution of aqueous-phase pathways increased at elevated ambient RH and remained constant at RH > 30 %. We also found that the concentrations of VOC precursors (e.g., toluene and benzene) and aerosol surface area acted as important factors in promoting NAC formation, and photolysis as an important loss pathway for nitrophenols.
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Holland, Rayne, Katya Seifert, Eric Saboya, M. Anwar H. Khan, Richard G. Derwent, and Dudley E. Shallcross. "Elucidating the Effects of COVID-19 Lockdowns in the UK on the O3-NOx-VOC Relationship." Atmosphere 15, no. 5 (May 16, 2024): 607. http://dx.doi.org/10.3390/atmos15050607.
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The unprecedented reductions in anthropogenic emissions over the COVID-19 lockdowns were utilised to investigate the response of ozone (O3) concentrations to changes in its precursors across various UK sites. Ozone, volatile organic compounds (VOCs) and NOx (NO+NO2) data were obtained for a 3-year period encompassing the pandemic period (January 2019–December 2021), as well as a pre-pandemic year (2017), to better understand the contribution of precursor emissions to O3 fluctuations. Compared with pre-lockdown levels, NO and NO2 declined by up to 63% and 42%, respectively, over the lockdown periods, with the most significant changes in pollutant concentrations recorded across the urban traffic sites. O3 levels correspondingly increased by up to 30%, consistent with decreases in the [NO]/[NO2] ratio for O3 concentration response. Analysis of the response of O3 concentrations to the NOx reductions suggested that urban traffic, suburban background and suburban industrial sites operate under VOC-limited regimes, while urban background, urban industrial and rural background sites are NOx-limited. This was in agreement with the [VOC]/[NOx] ratios determined for the London Marylebone Road (LMR; urban traffic) site and the Chilbolton Observatory (CO; rural background) site, which produced values below and above 8, respectively. Conversely, [VOC]/[NOx] ratios for the London Eltham (LE; suburban background) site indicated NOx-sensitivity, which may suggest the [VOC]/[NOx] ratio for O3 concentration response may have had a slight NOx-sensitive bias. Furthermore, O3 concentration response with [NO]/[NO2] and [VOC]/[NOx] were also investigated to determine their relevance and accuracy in identifying O3-NOx-VOC relationships across UK sites. While the results obtained via utilisation of these metrics would suggest a shift in photochemical regime, it is likely that variation in O3 during this period was primarily driven by shifts in oxidant (OX; NO2 + O3) equilibrium as a result of decreasing NO2, with increased O3 transported from Europe likely having some influence.
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Morin, S., R. Sander, and J. Savarino. "Simulation of the diurnal variations of the oxygen isotope anomaly (Δ<sup>17</sup>O) of reactive atmospheric species." Atmospheric Chemistry and Physics 11, no. 8 (April 19, 2011): 3653–71. http://dx.doi.org/10.5194/acp-11-3653-2011.
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Abstract. The isotope anomaly (Δ17O) of secondary atmospheric species such as nitrate (NO3−) or hydrogen peroxide (H2O2) has potential to provide useful constrains on their formation pathways. Indeed, the Δ17O of their precursors (NOx, HOx etc.) differs and depends on their interactions with ozone, which is the main source of non-zero Δ17O in the atmosphere. Interpreting variations of Δ17O in secondary species requires an in-depth understanding of the Δ17O of their precursors taking into account non-linear chemical regimes operating under various environmental settings. This article reviews and illustrates a series of basic concepts relevant to the propagation of the Δ17O of ozone to other reactive or secondary atmospheric species within a photochemical box model. We present results from numerical simulations carried out using the atmospheric chemistry box model CAABA/MECCA to explicitly compute the diurnal variations of the isotope anomaly of short-lived species such as NOx and HOx. Using a simplified but realistic tropospheric gas-phase chemistry mechanism, Δ17O was propagated from ozone to other species (NO, NO2, OH, HO2, RO2, NO3, N2O5, HONO, HNO3, HNO4, H2O2) according to the mass-balance equations, through the implementation of various sets of hypotheses pertaining to the transfer of Δ17O during chemical reactions. The model results confirm that diurnal variations in Δ17O of NOx predicted by the photochemical steady-state relationship during the day match those from the explicit treatment, but not at night. Indeed, the Δ17O of NOx is "frozen" at night as soon as the photolytical lifetime of NOx drops below ca. 10 min. We introduce and quantify the diurnally-integrated isotopic signature (DIIS) of sources of atmospheric nitrate and H2O2, which is of particular relevance to larger-scale simulations of Δ17O where high computational costs cannot be afforded.
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Cheng, Shan, Kehui Yao, Hong Tian, Ting Yang, and Lianghui Chen. "Synergistic Catalytic Effects on Nitrogen Transformation during Biomass Pyrolysis: A Focus on Proline as a Model Compound." Molecules 29, no. 13 (June 30, 2024): 3118. http://dx.doi.org/10.3390/molecules29133118.
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To investigate the control mechanisms of NOx precursors and the synergistic effects of composite catalysts during proline pyrolysis, a systematic series of experiments was conducted utilizing composite catalysts with varying Fe-Ca ratios. Product distribution analysis was employed to elucidate the catalysts’ mechanisms in reducing NOx precursor emissions. The synergistic interactions between Fe and Ca were quantitatively assessed through comparative theoretical and experimental release calculations. The results indicate that an increase in the Fe content in the catalyst led to a rise in amine concentrations from 0.9% to 2.95%, implying that Fe facilitates the generation of amine-N through ring-opening and substitution reactions. When the Fe to Ca ratio was balanced at 1:1, nitrogen predominantly participated in the formation of purines via cyclization and substitution reactions. Additionally, all composite catalysts exhibited a suppressive effect on the release of NOx precursors, attributed to their significant enhancement of solid product retention. Fe-Ca composite catalyst synergistically inhibits the release of gaseous nitrogen. Notably, the strongest synergistic effect was observed with a 1:3 Fe to Ca ratio, which reduced the release of NH3 by 38.7% and HCN by 53.6% during proline pyrolysis. This study offers valuable insights into the control of NOx precursors and the optimization of nitrogen-rich biomass pyrolysis processes.
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Marais, E. A., D. J. Jacob, J. L. Jimenez, P. Campuzano-Jost, D. A. Day, W. Hu, J. Krechmer, et al. "Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the Southeast United States and co-benefit of SO<sub>2</sub> emission controls." Atmospheric Chemistry and Physics Discussions 15, no. 21 (November 13, 2015): 32005–47. http://dx.doi.org/10.5194/acpd-15-32005-2015.
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Abstract. Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake probabilities (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the Southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx ≡ NO + NO2) over the Southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of OA and formaldehyde (a product of isoprene oxidation). The yield is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the indirect effect of sulfate on aerosol acidity and volume, rather than a direct mechanistic role for sulfate. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation), but decrease as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US EPA projects 2013–2025 decreases in anthropogenic emissions of 34 % for NOx (leading to 7 % increase in isoprene SOA) and 48 % for SO2 (35 % decrease in isoprene SOA). The combined projected decreases in NOx and SO2 emissions reduce isoprene SOA yields from 3.3 to 2.3 %. Reducing SO2 emissions decreases sulfate and isoprene SOA by a similar magnitude, representing a factor of 2 co-benefit for PM2.5 from SO2 emission controls.
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Schroeder, Jason R., Chenxia Cai, Jin Xu, David Ridley, Jin Lu, Nancy Bui, Fang Yan, and Jeremy Avise. "Changing ozone sensitivity in the South Coast Air Basin during the COVID-19 period." Atmospheric Chemistry and Physics 22, no. 19 (October 10, 2022): 12985–3000. http://dx.doi.org/10.5194/acp-22-12985-2022.
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Abstract. The South Coast Air Basin (SoCAB), which includes the city of Los Angeles and is home to more than 15 million people, frequently experiences ozone (O3) levels that exceed ambient air quality standards. While strict regulation of O3 precursors has dramatically improved air quality over the past 50 years, the region has seen limited improvement in O3 over the past decade despite continued reductions in precursor emissions. One contributing factor to the recent lack of improvement is a gradual transition of the underlying photochemical environment from a VOC-limited regime (where VOC denotes volatile organic compound) towards an NOx-limited one. The changes in human activity prompted by COVID-19-related precautions in spring and summer of 2020 exacerbated these existing changes in the O3 precursor environment. Analyses of sector-wide changes in activity indicate that emissions of NOx decreased by 15 %–20 % during spring (April–May) and by 5 %–10 % during summer (June–July) relative to expected emissions for 2020, largely due to changes in mobile-source activity. Historical trend analysis from two indicators of O3 sensitivity (the satellite HCHO/NO2 ratio and the O3 weekend/weekday ratio) revealed that spring of 2020 was the first year on record to be on average NOx-limited, while the “transitional” character of recent summers became NOx-limited due to COVID-19-related NOx reductions in 2020. Model simulations performed with baseline and COVID-19-adjusted emissions capture this change to an NOx-limited environment and suggest that COVID-19-related emission reductions were responsible for a 0–2 ppb decrease in O3 over the study period. Reaching NOx-limited territory is an important regulatory milestone, and this study suggests that deep reductions in NOx emissions (in excess of those observed in this study) would be an effective pathway toward long-term O3 reductions.
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Marais, E. A., D. J. Jacob, J. L. Jimenez, P. Campuzano-Jost, D. A. Day, W. Hu, J. Krechmer, et al. "Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO<sub>2</sub> emission controls." Atmospheric Chemistry and Physics 16, no. 3 (February 11, 2016): 1603–18. http://dx.doi.org/10.5194/acp-16-1603-2016.
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Abstract. Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx ≡ NO + NO2) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the effect of sulfate on aerosol acidity and volume. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation), but decrease more strongly as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US Environmental Protection Agency (EPA) projects 2013–2025 decreases in anthropogenic emissions of 34 % for NOx (leading to a 7 % increase in isoprene SOA) and 48 % for SO2 (35 % decrease in isoprene SOA). Reducing SO2 emissions decreases sulfate and isoprene SOA by a similar magnitude, representing a factor of 2 co-benefit for PM2.5 from SO2 emission controls.
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Seltzer, K. M., W. Vizuete, and B. H. Henderson. "Evaluation of updated nitric acid chemistry on ozone precursors and radiative effects." Atmospheric Chemistry and Physics Discussions 15, no. 3 (February 3, 2015): 3219–55. http://dx.doi.org/10.5194/acpd-15-3219-2015.
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Abstract. This study shows that revising the reaction rate of NO2 + HO• → HNO3 improves simulated nitrogen partitioning and adjusts the simulated radiative effects of several radiative forcing variables. Both laboratory and field study analysis have found that the reaction rate should be reduced by 13–30% from current recommendations. We evaluate the GEOS-Chem model over North America with and without the recommended update. Revising the NO2 + HO• → HNO3 rate coefficient improves model performance by increasing NOx concentrations in the upper troposphere and decreasing HNO3 throughout the troposphere. The downward revision of the NO2 + HO• → HNO3 rate increases the lifetime of NOx, increases O3 concentrations and increases the simulated radiative effects of tropospheric ozone. These findings demonstrate the influence the rate revision has on the composition of the atmosphere, the benefits it provides when compared to observations and the simulated radiative effects that the reduction induces.
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Li, Ruiyuan, Miaoqing Xu, Manchun Li, Ziyue Chen, Na Zhao, Bingbo Gao, and Qi Yao. "Identifying the spatiotemporal variations in ozone formation regimes across China from 2005 to 2019 based on polynomial simulation and causality analysis." Atmospheric Chemistry and Physics 21, no. 20 (October 19, 2021): 15631–46. http://dx.doi.org/10.5194/acp-21-15631-2021.
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Abstract. Ozone formation regimes are closely related to the ratio of volatile organic compounds (VOCs) to NOx. Different ranges of HCHO/NO2 indicate three formation regimes, including VOC-limited, transitional, and NOx-limited regimes. Due to the unstable interactions between a diversity of precursors, the range of the transitional regime, which plays a key role in identifying ozone formation regimes, remains unclear. To overcome the uncertainties from single models and the lack of reference data, we employed two models, polynomial simulation and convergent cross-mapping (CCM), to identify the ranges of HCHO/NO2 across China based on ground observations and remote sensing datasets. The ranges of the transitional regime estimated by polynomial simulation and CCM were [1.0, 1.9] and [1.0, 1.8]. Since 2013, the ozone formation regime has changed to the transitional and NOx-limited regime all over China, indicating that ozone concentrations across China were mainly controlled by NOx. However, despite the NO2 concentrations, HCHO concentrations continuously exert a positive influence on ozone concentrations under transitional and NOx-limited regimes. Under the circumstance of national NOx reduction policies, the increase in VOCs became the major driver for the soaring ozone pollution across China. For an effective management of ozone pollution across China, the emission reduction in VOCs and NOx should be equally considered.
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Savarino, J., W. C. Vicars, M. Legrand, S. Preunkert, B. Jourdain, M. M. Frey, A. Kukui, N. Caillon, and J. Gil Roca. "Oxygen isotope mass balance of atmospheric nitrate at Dome C, East Antarctica, during the OPALE campaign." Atmospheric Chemistry and Physics Discussions 15, no. 17 (September 7, 2015): 24041–83. http://dx.doi.org/10.5194/acpd-15-24041-2015.
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Abstract. Variations in the stable oxygen isotope composition of atmospheric nitrate act as novel tools for studying oxidative processes taking place in the troposphere. They provide both qualitative and quantitative constraints on the pathways determining the fate of atmospheric nitrogen oxides (NO + NO2 = NOx). The unique and distinctive 17O-excess (Δ17O = δ17O − 0.52 × δ18O) of ozone, which is transferred to NOx via oxidation, is a particularly useful isotopic fingerprint in studies of NOx transformations. Constraining the propagation of 17O-excess within the NOx cycle is critical in polar areas where there exists the possibility of extending atmospheric investigations to the glacial/interglacial time scale using deep ice core records of nitrate. Here we present measurements of the comprehensive isotopic composition of atmospheric nitrate collected at Dome C (East Antarctic plateau) during the austral summer of 2011/12. Nitrate isotope analysis has been here combined for the first time with key precursors involved in nitrate production (NOx, O3, OH, HO2, RO2, etc.) and direct observations of the transferrable Δ17O of surface ozone, which was measured at Dome C throughout 2012 using our recently developed analytical approach. Assuming that nitrate is mainly produced in Antarctica in summer through the OH + NO2 pathway and using concurrent measurements of OH and NO2, we calculated a Δ17O signature for nitrate in the order of (21–22 ± 3) ‰. These values are lower than the measured values that ranged between 27 and 31 ‰. This discrepancy between expected and observed Δ17O(NO3−) values suggests the existence of an unknown process that contributes significantly to the atmospheric nitrate budget over this east Antarctic region.
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Savarino, Joël, William C. Vicars, Michel Legrand, Suzanne Preunkert, Bruno Jourdain, Markus M. Frey, Alexandre Kukui, Nicolas Caillon, and Jaime Gil Roca. "Oxygen isotope mass balance of atmospheric nitrate at Dome C, East Antarctica, during the OPALE campaign." Atmospheric Chemistry and Physics 16, no. 4 (March 3, 2016): 2659–73. http://dx.doi.org/10.5194/acp-16-2659-2016.
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Abstract. Variations in the stable oxygen isotope composition of atmospheric nitrate act as novel tools for studying oxidative processes taking place in the troposphere. They provide both qualitative and quantitative constraints on the pathways determining the fate of atmospheric nitrogen oxides (NO + NO2 = NOx). The unique and distinctive 17O excess (Δ17O = δ17O − 0.52 × δ18O) of ozone, which is transferred to NOx via oxidation, is a particularly useful isotopic fingerprint in studies of NOx transformations. Constraining the propagation of 17O excess within the NOx cycle is critical in polar areas, where there exists the possibility of extending atmospheric investigations to the glacial–interglacial timescale using deep ice core records of nitrate. Here we present measurements of the comprehensive isotopic composition of atmospheric nitrate collected at Dome C (East Antarctic Plateau) during the austral summer of 2011/2012. Nitrate isotope analysis has been here combined for the first time with key precursors involved in nitrate production (NOx, O3, OH, HO2, RO2, etc.) and direct observations of the transferrable Δ17O of surface ozone, which was measured at Dome C throughout 2012 using our recently developed analytical approach. Assuming that nitrate is mainly produced in Antarctica in summer through the OH + NO2 pathway and using concurrent measurements of OH and NO2, we calculated a Δ17O signature for nitrate on the order of (21–22 ± 3) ‰. These values are lower than the measured values that ranged between 27 and 31 ‰. This discrepancy between expected and observed Δ17O(NO3−) values suggests the existence of an unknown process that contributes significantly to the atmospheric nitrate budget over this East Antarctic region. However, systematic errors or false isotopic balance transfer functions are not totally excluded.
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Ren, Qiangqiang. "NOx and N2O precursors from biomass pyrolysis." Journal of Thermal Analysis and Calorimetry 115, no. 1 (May 21, 2013): 881–85. http://dx.doi.org/10.1007/s10973-013-3238-5.
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Nussbaumer, Clara M., Horst Fischer, Jos Lelieveld, and Andrea Pozzer. "What controls ozone sensitivity in the upper tropical troposphere?" Atmospheric Chemistry and Physics 23, no. 19 (October 11, 2023): 12651–69. http://dx.doi.org/10.5194/acp-23-12651-2023.
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Abstract. Ozone is an important contributor to the radiative energy budget of the upper troposphere (UT). Therefore, observing and understanding the processes contributing to ozone production are important for monitoring the progression of climate change. Nitrogen oxides (NOx ≡ NO + NO2) and volatile organic compounds (VOCs) are two main tropospheric precursors to ozone formation. Depending on their abundances, ozone production can be sensitive to changes in either of these two precursors. Here, we focus on processes contributing to ozone chemistry in the upper tropical troposphere between 30∘ S and 30∘ N latitude, where changes in ozone have a relatively large impact on anthropogenic radiative forcing. Based on modeled trace gas mixing ratios and meteorological parameters simulated by the ECHAM5/MESSy2 Atmospheric Chemistry (EMAC) general circulation model, we analyze a variety of commonly applied metrics including ozone production rates (P(O3)), the formaldehyde (HCHO) to NO2 ratio and the share of methyl peroxy radicals (CH3O2) forming HCHO (α(CH3O2)) for their ability to describe the chemical regime. We show that the distribution of trace gases in the tropical UT is strongly influenced by the varying locations of deep convection throughout the year, and we observe peak values for NOx and P(O3) over the continental areas of South America and Africa where lightning is frequent. We find that P(O3) and its response to NO is unsuitable for determining the dominant regime in the upper troposphere. Instead, α(CH3O2) and the HCHO/NO2 ratio in combination with ambient NO levels perform well as metrics to indicate whether NOx or VOC sensitivity is prevalent. We show that effectively only the knowledge of the availability of NO and HO2 is required to adequately represent O3 precursors and its sensitivity towards them. A sensitivity study with halving, doubling and excluding lightning NOx demonstrates that lightning and its distribution in the tropics are the major determinants of the chemical regimes and ozone formation in the upper tropical troposphere.
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Elshorbany, Yasin, Jerald R. Ziemke, Sarah Strode, Hervé Petetin, Kazuyuki Miyazaki, Isabelle De Smedt, Kenneth Pickering, et al. "Tropospheric ozone precursors: global and regional distributions, trends, and variability." Atmospheric Chemistry and Physics 24, no. 21 (November 5, 2024): 12225–57. http://dx.doi.org/10.5194/acp-24-12225-2024.
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Abstract. Tropospheric ozone results from in situ chemical formation and stratosphere–troposphere exchange (STE), with the latter being more important in the middle and upper troposphere than in the lower troposphere. Ozone photochemical formation is nonlinear and results from the oxidation of methane and non-methane hydrocarbons (NMHCs) in the presence of nitrogen oxide (NOx=NO+NO2). Previous studies showed that O3 short- and long-term trends are nonlinearly controlled by near-surface anthropogenic emissions of carbon monoxide (CO), volatile organic compounds (VOCs), and nitrogen oxides, which may also be impacted by the long-range transport (LRT) of O3 and its precursors. In addition, several studies have demonstrated the important role of STE in enhancing ozone levels, especially in the midlatitudes. In this article, we investigate tropospheric ozone spatial variability and trends from 2005 to 2019 and relate those to ozone precursors on global and regional scales. We also investigate the spatiotemporal characteristics of the ozone formation regime in relation to ozone chemical sources and sinks. Our analysis is based on remote sensing products of the tropospheric column of ozone (TrC-O3) and its precursors, nitrogen dioxide (TrC-NO2), formaldehyde (TrC-HCHO), and total column CO (TC-CO), as well as ozonesonde data and model simulations. Our results indicate a complex relationship between tropospheric ozone column levels, surface ozone levels, and ozone precursors. While the increasing trends of near-surface ozone concentrations can largely be explained by variations in VOC and NOx concentration under different regimes, TrC-O3 may also be affected by other variables such as tropopause height and STE as well as LRT. Decreasing or increasing trends in TrC-NO2 have varying effects on TrC-O3, which is related to the different local chemistry in each region. We also shed light on the contribution of NOx lightning and soil NO and nitrous acid (HONO) emissions to trends of tropospheric ozone on regional and global scales.
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Jiang, Z., J. R. Worden, D. B. A. Jones, J. T. Lin, W. W. Verstraeten, and D. K. Henze. "Constraints on Asian ozone using Aura TES, OMI and Terra MOPITT." Atmospheric Chemistry and Physics 15, no. 1 (January 8, 2015): 99–112. http://dx.doi.org/10.5194/acp-15-99-2015.
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Abstract. Rapid industrialization in Asia in the last two decades has resulted in a significant increase in Asian ozone (O3) precursor emissions with likely a corresponding increase in the export of O3 and its precursors. However, the relationship between this increasing O3, the chemical environment, O3 production efficiency, and the partitioning between anthropogenic and natural precursors is unclear. In this work, we use satellite measurements of O3, CO and NO2 from TES (Tropospheric Emission Spectrometer), MOPITT (Measurement of Pollution In The Troposphere) and OMI (Ozone Monitoring Instrument) to quantify O3 precursor emissions for 2006 and their impact on free tropospheric O3 over northeastern Asia, where pollution is typically exported globally due to strong westerlies. Using the GEOS-Chem (Goddard Earth Observing System Chemistry) global chemical transport model, we test the modeled seasonal and interannual variation of O3 based on prior and updated O3 precursor emissions where the updated emissions of CO and NOx are based on satellite measurements of CO and NO2. We show that the observed TES O3 variability and amount are consistent with the model for these updated emissions. However, there is little difference in the modeled ozone between the updated and prior emissions. For example, for the 2006 June time period, the prior and posterior NOx emissions were 14% different over China but the modeled ozone in the free troposphere was only 2.5% different. Using the adjoint of GEOS-Chem we partition the relative contributions of natural and anthropogenic sources to free troposphere O3 in this region. We find that the influence of lightning NOx in the summer is comparable to the contribution from surface emissions but smaller for other seasons. China is the primary contributor of anthropogenic CO, emissions and their export during the summer. While the posterior CO emissions improved the comparison between model and TES by 32%, on average, this change also had only a small effect on the free tropospheric ozone. Our results show that the influence of India and southeastern Asia emissions on O3 pollution export to the northwestern Pacific is sizeable, comparable with Chinese emissions in winter, about 50% of Chinese emissions in spring and fall, and approximately 20% of the emissions in the summer.
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Wu, Luolin, Jian Hang, Xuemei Wang, Min Shao, and Cheng Gong. "APFoam 1.0: integrated computational fluid dynamics simulation of O<sub>3</sub>–NO<sub><i>x</i></sub>–volatile organic compound chemistry and pollutant dispersion in a typical street canyon." Geoscientific Model Development 14, no. 7 (July 28, 2021): 4655–81. http://dx.doi.org/10.5194/gmd-14-4655-2021.
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Abstract. Urban air quality issues are closely related to human health and economic development. In order to investigate street-scale flow and air quality, this study developed the atmospheric photolysis calculation framework (APFoam 1.0), an open-source computational fluid dynamics (CFD) code based on OpenFOAM, which can be used to examine microscale reactive pollutant formation and dispersion in an urban area. The chemistry module of APFoam has been modified by adding five new types of reactions, which can implement the atmospheric photochemical mechanism (full O3–NOx–volatile organic compound chemistry) coupled with a CFD model. Additionally, the model, including the photochemical mechanism (CS07A), air flow, and pollutant dispersion, has been validated and shows good agreement with SAPRC modeling and wind tunnel experimental data, indicating that APFoam has sufficient ability to study urban turbulence and pollutant dispersion characteristics. By applying APFoam, O3–NOx–volatile organic compound (VOC) formation processes and dispersion of the reactive pollutants were analyzed in an example of a typical street canyon (aspect ratio H/W=1). The comparison of chemistry mechanisms shows that O3 and NO2 are underestimated, while NO is overestimated if the VOC reactions are not considered in the simulation. Moreover, model sensitivity cases reveal that 82 %–98 % and 75 %–90 % of NO and NO2, respectively, are related to the local vehicle emissions, which is verified as the dominant contributor to local reactive pollutant concentration in contrast to background conditions. In addition, a large amount of NOx emissions, especially NO, is beneficial to the reduction of O3 concentrations since NO consumes O3. Background precursors (NOx/VOCs) from boundary conditions only contribute 2 %–16 % and 12 %–24 % of NO and NO2 concentrations and raise O3 concentrations by 5 %–9 %. Weaker ventilation conditions could lead to the accumulation of NOx and consequently a higher NOx concentration but lower O3 concentration due to the stronger NO titration effect, which would consume O3. Furthermore, in order to reduce the reactive pollutant concentrations under the odd–even license plate policy (reduce 50 % of the total vehicle emissions), vehicle VOC emissions should be reduced by at least another 30 % to effectively lower O3, NO, and NO2 concentrations at the same time. These results indicate that the examination of the precursors (NOx and VOCs) from both traffic emissions and background boundaries is the key point for understanding O3–NOx–VOCs chemistry mechanisms better in street canyons and providing effective guidelines for the control of local street air pollution.
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Lei, H., and J. X. L. Wang. "Sensitivities of NO<sub>x</sub> transformation and the effects on surface ozone and nitrate." Atmospheric Chemistry and Physics 14, no. 3 (February 5, 2014): 1385–96. http://dx.doi.org/10.5194/acp-14-1385-2014.
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Abstract. As precursors to tropospheric ozone and nitrate, nitrogen oxide (NOx) in the present atmosphere and its transformation in response to emission and climate perturbations are studied by using the CAM-Chem model and air quality measurements from the National Emissions Inventory (NEI), Clean Air Status and Trends Network (CASTNET), and Environmental Protection Agency Air Quality System (EPA AQS). It is found that NOx transformations in present atmospheric conditions show different sensitivities over industrial and non-industrial regions. As a result, the surface ozone and nitrate formations can be divided into several regimes associated with the dominant emission types and relative levels of NOx and volatile organic compounds (VOC). Ozone production in industrial regions (the main NOx emission source areas) increases in warmer conditions and slightly decreases following an increase in NOx emissions due to NOx titration, which is opposite to the response in non-industrial regions. The ozone decrease following a temperature increase in non-industrial regions indicates that ozone production in regions that lack NOx emission sources may be sensitive to NOx transformation in remote source regions. The increase in NO2 from NOx titration over industrial regions results in an increase rate of total nitrate that remains higher than the increase rate of NOx emissions. The presented findings indicate that a change in the ozone concentration is more directly affected by changes in climate and precursor emissions, while a change in the nitrate concentration is affected by local ozone production types and their seasonal transfer. The sensitivity to temperature perturbations shows that a warmer climate accelerates the decomposition of odd nitrogen (NOy) during the night. As a result, the transformation rate of NOx to nitrate decreases. Examinations of the historical emissions and air quality records of a typical NOx-limited area, such as Atlanta and a VOC-limited area, such as Los Angeles further confirm the conclusions drawn from the modeling experiments.
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Flowerday, Callum E., Ryan Thalman, and Jaron C. Hansen. "Local and Regional Contributions to Tropospheric Ozone Concentrations." Atmosphere 14, no. 8 (August 9, 2023): 1262. http://dx.doi.org/10.3390/atmos14081262.
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The Wasatch Front in Utah, USA is currently a non-attainment area for ozone according to the Environmental Protection Agency’s (EPA) National Ambient Air Quality Standards (NAAQS). Nitrogen oxides (NOx = NO2 + NO) and volatile organic compounds (VOCs) in the presence of sunlight lead to ozone formation in the troposphere. When the rate of oxidant production, defined as the sum of O3 and NO2, is faster than the rate of NOx production, a region is said to be NOx-limited and ozone formation will be limited by the concentration of NOx species in the region. The inverse of this situation makes the region VOC-limited. Knowing if a region is NOx-limited or VOC-limited can aid in generating effective mitigation strategies. Understanding the background or regional contributions to ozone in a region, whether it be from the transport of precursors or of ozone, provides information about the lower limit for ozone concentrations that a region can obtain with regulation of local precursors. In this paper, measured oxidant and NOx concentrations are analyzed from 14 counties in the state of Utah to calculate the regional and local contributions to ozone for each region. This analysis is used to determine the nature of the atmosphere in each county by determining if the region is VOC- or NOx-limited. Furthermore, this analysis is performed for each county for the years 2012 and 2022 to determine if there has been a change in the oxidative nature and quantify the regional and local contributions to ozone over a 10-year period. All studied counties—except for Washington County—in Utah were found to be VOC-limited in 2012. This shifted in 2022 to most counties being either in a transitional state or being NOx-limited. Local contributions to ozone increased in two major counties, Cache and Salt Lake Counties, but decreased in Carbon, Davis, Duchesne, Uinta, Utah, Washington, and Weber Counties. Generally, the regional contributions to oxidant concentrations decreased across the state. A summertime spike in both regional and local contributions to oxidants was seen. Smoke from wildfires was seen to increase the regional contributions to oxidants and shift the local regime to be more NOx-limited.
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Marécal, V., E. D. Rivière, G. Held, S. Cautenet, and S. Freitas. "Modelling study of the impact of deep convection on the UTLS air composition – Part I: Analysis of ozone precursors." Atmospheric Chemistry and Physics Discussions 5, no. 5 (September 23, 2005): 9127–68. http://dx.doi.org/10.5194/acpd-5-9127-2005.
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Abstract. The aim of this work is to study the local impact of deep convection on the upper troposphere/lower stratosphere air composition. For this purpose, we performed a 42-h simulation of a severe convective event near Bauru, in the central State of São Paulo (Brazil), with the 3-D mesoscale model RAMS coupled on-line with a chemistry model. The meteorological results of the simulation are evaluated using comparisons with near surface measurements of wind and temperature and with surface rainfall rates derived from radar observations. These comparisons show that the model produces meteorological fields consistent with the observations. This present paper (Part I) is devoted to the analysis of the ozone precursors in the upper troposphere/lower stratosphere: CO, NOx (=NO+NO2) and non-methane volatile organic compounds. The simulation results show that the distribution of CO with altitude is closely related to the upward convective motions and consecutive outflow at the top of the convective cells leading to a bulge of CO between 7 km altitude and the cold point tropopause (around 17km altitude). The model results for CO are consistent with satellite-borne measurements in the 700–500 hPa layer. The simulation also indicates enhanced amounts of NOx up to 2 ppbv in the 7–17 km altitude layer. These NOx concentrations are mainly produced by the lightning associated with the intense convective activity. Stratospheric NOx are not affected by the tropospheric NOx since there is, on average, no significant upward NOx flux through the tropopause. For non-methane volatile organic compounds, the convective activity tends to significantly increase the amount of ozone precursors in the 7–17 km layer by dynamical effects as for CO. During daytime, this bulge is largely reduced in the upper part of the layer for reactive species, such as isoprene, ethene and propene, since they undergo chemical loss. This loss is mainly due to their reactions with OH, OH mixing ratio being significantly increased during the daytime by the production of NOx by lightning. The bulges of ozone precursors in the upper troposphere are likely to be of importance in the ozone budget in the upper troposphere and lower stratosphere. This issue is discussed in Part II of this series of papers.
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Seltzer, K. M., W. Vizuete, and B. H. Henderson. "Evaluation of updated nitric acid chemistry on ozone precursors and radiative effects." Atmospheric Chemistry and Physics 15, no. 10 (May 29, 2015): 5973–86. http://dx.doi.org/10.5194/acp-15-5973-2015.
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Abstract. This study shows that revising the reaction rate of NO2 + HO· → HNO3 improves simulated nitrogen partitioning and changes the simulated radiative effects of several short-lived climate forcers (SLCF). Both laboratory and field study analyses have found that the reaction rate should be reduced by 13–30% from current recommendations. We evaluate the GEOS-Chem model over North America with and without the recommended update using observations from the Intercontinental Chemical Transport Experiment – North America (INTEX-NA) Phase A campaign. Revising the NO2 + HO· → HNO3 rate coefficient improves model performance of oxidized nitrogen partitioning by increasing NOx concentrations in the upper troposphere and decreasing HNO3 throughout the troposphere. The increase in NOx concentrations has a corresponding global increase in O3 concentrations and local increases in sulfate aerosols, causing a perturbation in simulated radiative effects. These findings demonstrate the positive influence the mechanism update has on the partitioning of oxidized nitrogen species, the benefits it provides when compared to aircraft observations, and the simulated radiative effects that the reduction induces.
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Kusumaningtyas, Sheila Dewi Ayu, Kenichi Tonokura, Dodo Gunawan, and Windy Iriana. "Long-term trends of ozone precursors and ozone sensitivity in Jakarta Metropolitan Area: A view from space." E3S Web of Conferences 485 (2024): 06011. http://dx.doi.org/10.1051/e3sconf/202448506011.
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Jakarta Metropolitan Area (JMA) is an urban agglomeration in Indonesia where the air quality has dramatically changed from relatively clean to polluted. Economic growth, increased population, and village-to-city expansion marked the development of Jakarta and the satellite cities surrounding it, such as Bogor, Depok, Tangerang, and Bekasi. In line with human activities, large amounts of air pollutants are emitted and affect human health and vegetation. Ozone (O3) is a secondary air pollutant formed from volatile organic compounds (VOCs) and nitrogen oxides (NOx). This study aims to investigate the long-term trend of ozone precursors and ozone sensitivity in JMA from space. Trends analysis is studied using quantile regression. We used NO2 and formaldehyde (HCHO) column density from the Ozone Monitoring Instrument (OMI) aboard Aura Satellite from 2011 to 2022. Ozone sensitivity is derived from the ratio of HCHO and NO2 (FNR). The results show an upward trend in HCHO and a slight NO2 downward over JMA. In general, FNR changed from a predominantly VOC-limited regime in urban JMA to a transitional regime suggesting control of VOC and NOx is needed to reduce ozone concentration. Meanwhile, FNR in suburban and rural areas such as Bogor is toward a more NOx-limited regime.
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Ianniello, Antonietta, Roberto Salzano, Rosamaria Salvatori, Giulio Esposito, Francesca Spataro, Mauro Montagnoli, Rosanna Mabilia, and Antonello Pasini. "Nitrogen Oxides (NOx) in the Arctic Troposphere at Ny-Ålesund (Svalbard Islands): Effects of Anthropogenic Pollution Sources." Atmosphere 12, no. 7 (July 13, 2021): 901. http://dx.doi.org/10.3390/atmos12070901.
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Atmospheric measurements of nitrogen oxides (NOx = NO + NO2), ozone (O3) and other constituents were carried out during three field campaigns (29 March–30 April 2010, 1–26 April 2011, 18 May–8 October 2015) at Ny-Ålesund. The study focused on the variability of important O3 precursors, such as NOx, in the Arctic troposphere, and on the impact from anthropogenic sources on their measured concentrations: higher NO and NO2 levels were mostly associated with the lowest wind speeds and northern directions, indicating local pollution. Long-range transported sources from Russia and Europe were also identified with an occurrence of high NOx levels. Several ozone depletion events were observed and associated to winds blowing from the north-west direction (Arctic Ocean). Most of these events were connected to the lower NO and NO2 concentrations. Measurements of halogen and low molecular weight carbonyl compounds in 2010 and 2011, respectively, showed variable effects during the ozone depletion events. Other data, such as high time-resolved radon progeny measurements, were used in 2015 to identify source tracking and transport of air masses, local effects and atmospheric stability dynamics that could influence the NOx concentrations at Ny-Ålesund.
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Cheng, Xi, Yong Jie Li, Yan Zheng, Keren Liao, Theodore K. Koenig, Yanli Ge, Tong Zhu, Chunxiang Ye, Xinghua Qiu, and Qi Chen. "Oxygenated organic molecules produced by low-NOx photooxidation of aromatic compounds: contributions to secondary organic aerosol and steric hindrance." Atmospheric Chemistry and Physics 24, no. 4 (February 19, 2024): 2099–112. http://dx.doi.org/10.5194/acp-24-2099-2024.
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Abstract. Oxygenated organic molecules (OOMs) produced by the oxidation of aromatic compounds are key components of secondary organic aerosol (SOA) in urban environments. The steric effects of substitutions and rings and the role of key reaction pathways in altering the OOM distributions remain unclear because of the lack of systematic multi-precursor study over a wide range of OH exposure. In this study, we conducted flow-tube experiments and used the nitrate adduct time-of-flight chemical ionization mass spectrometer (NO3--TOF-CIMS) to measure the OOMs produced by the photooxidation of six key aromatic precursors under low-NOx conditions. For single aromatic precursors, the detected OOM peak clusters show an oxygen atom difference of one or two, indicating the involvement of multi-step auto-oxidation and alkoxy radical pathways. Multi-generation OH oxidation is needed to explain the diverse hydrogen numbers in the observed formulae. In particular, for double-ring precursors at higher OH exposure, multi-generation OH oxidation may have significantly enriched the dimer formulae. The results suggest that methyl substitutions in precursor lead to less fragmented OOM products, while the double-ring structure corresponds to less efficient formation of closed-shell monomeric and dimeric products, both highlighting significant steric effects of precursor molecular structure on the OOM formation. Naphthalene-derived OOMs however have lower volatilities and greater SOA contributions than the other-type of OOMs, which may be more important in initial particle growth. Overall, the OOMs identified by the NO3--TOF-CIMS may have contributed up to 30.0 % of the measured SOA mass, suggesting significant mass contributions of less oxygenated, undetected semi-volatile products. Our results highlight the key roles of progressive OH oxidation, methyl substitution and ring structure in the OOM formation from aromatic precursors, which need to be considered in future model developments to improve the model performance for organic aerosol.
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Tan, Zhaofeng, Keding Lu, Meiqing Jiang, Rong Su, Hongli Wang, Shengrong Lou, Qingyan Fu, et al. "Daytime atmospheric oxidation capacity in four Chinese megacities during the photochemically polluted season: a case study based on box model simulation." Atmospheric Chemistry and Physics 19, no. 6 (March 20, 2019): 3493–513. http://dx.doi.org/10.5194/acp-19-3493-2019.
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Abstract. Atmospheric oxidation capacity is the basis for converting freshly emitted substances into secondary products and is dominated by reactions involving hydroxyl radicals (OH) during daytime. In this study, we present in situ measurements of ROx radical (hydroxy OH, hydroperoxy HO2, and organic peroxy RO2) precursors and products; the measurements are carried out in four Chinese megacities (Beijing, Shanghai, Guangzhou, and Chongqing) during photochemically polluted seasons. The atmospheric oxidation capacity is evaluated using an observation-based model and radical chemistry precursor measurements as input. The radical budget analysis illustrates the importance of HONO and HCHO photolysis, which account for ∼50 % of the total primary radical sources. The radical propagation is efficient due to abundant NO in urban environments. Hence, the production rate of secondary pollutants, that is, ozone (and fine-particle precursors (H2SO4, HNO3, and extremely low volatility organic compounds, ELVOCs) is rapid, resulting in secondary air pollution. The ozone budget demonstrates its high production in urban areas; also, its rapid transport to downwind areas results in rapid increase in local ozone concentrations. The O3–NOx–VOC (volatile organic compound) sensitivity tests show that ozone production is VOC-limited and that alkenes and aromatics should be mitigated first for ozone pollution control in the four studied megacities. In contrast, NOx emission control (that is, a decrease in NOx) leads to more severe ozone pollution. With respect to fine-particle pollution, the role of the HNO3–NO3 partitioning system is investigated using a thermal dynamic model (ISORROPIA 2). Under high relative humidity (RH) and ammonia-rich conditions, nitric acid converts into nitrates. This study highlights the efficient radical chemistry that maintains the atmospheric oxidation capacity in Chinese megacities and results in secondary pollution characterized by ozone and fine particles.
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Liu, Lei, Xiuying Zhang, Wen Xu, Xuejun Liu, Yi Li, Xuehe Lu, Yuehan Zhang, and Wuting Zhang. "Temporal characteristics of atmospheric ammonia and nitrogen dioxide over China based on emission data, satellite observations and atmospheric transport modeling since 1980." Atmospheric Chemistry and Physics 17, no. 15 (August 7, 2017): 9365–78. http://dx.doi.org/10.5194/acp-17-9365-2017.
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Abstract. China is experiencing intense air pollution caused in large part by anthropogenic emissions of reactive nitrogen (Nr). Atmospheric ammonia (NH3) and nitrogen dioxide (NO2) are the most important precursors for Nr compounds (including N2O5, HNO3, HONO and particulate NO3− and NH4+) in the atmosphere. Understanding the changes in NH3 and NO2 has important implications for the regulation of anthropogenic Nr emissions and is a requirement for assessing the consequence of environmental impacts. We conducted the temporal trend analysis of atmospheric NH3 and NO2 on a national scale since 1980 based on emission data (during 1980–2010), satellite observation (for NH3 since 2008 and for NO2 since 2005) and atmospheric chemistry transport modeling (during 2008–2015).Based on the emission data, during 1980–2010, significant continuous increasing trends in both NH3 and NOx were observed in REAS (Regional Emission inventory in Asia, for NH3 0.17 and for NOx 0.16 kg N ha−1 yr−2) and EDGAR (Emissions Database for Global Atmospheric Research, for NH3 0.24 and for NOx 0.17 kg N ha−1 yr−2) over China. Based on the satellite data and atmospheric chemistry transport model (CTM) MOZART-4 (Model for Ozone and Related chemical Tracers, version 4), the NO2 columns over China increased significantly from 2005 to 2011 and then decreased significantly from 2011 to 2015; the satellite-retrieved NH3 columns from 2008 to 2014 increased at a rate of 2.37 % yr−1. The decrease in NO2 columns since 2011 may result from more stringent strategies taken to control NOx emissions during the 12th Five Year Plan, while no control policy has focused on NH3 emissions. Our findings provided an overall insight into the temporal trends of both NO2 and NH3 since 1980 based on emission data, satellite observations and atmospheric transport modeling. These findings can provide a scientific background for policy makers that are attempting to control atmospheric pollution in China. Moreover, the multiple datasets used in this study have implications for estimating long-term Nr deposition datasets to assess its impact on soil, forest, water and greenhouse balance.
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Muñoz, Verónica, Fatima Maria Zanon Zotin, and Luz Amparo Palacio. "Copper–aluminum hydrotalcite type precursors for NOx abatement." Catalysis Today 250 (July 2015): 173–79. http://dx.doi.org/10.1016/j.cattod.2014.06.004.
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Xu, Weiqi, Masayuki Takeuchi, Chun Chen, Yanmei Qiu, Conghui Xie, Wanyun Xu, Nan Ma, Douglas R. Worsnop, Nga Lee Ng, and Yele Sun. "Estimation of particulate organic nitrates from thermodenuder–aerosol mass spectrometer measurements in the North China Plain." Atmospheric Measurement Techniques 14, no. 5 (May 21, 2021): 3693–705. http://dx.doi.org/10.5194/amt-14-3693-2021.
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Abstract. Particulate organic nitrates (pON) are an important component of secondary organic aerosol in biogenic-emission-dominant environments and play a critical role in NOx cycles. However, estimation of pON has been a challenge in polluted environments, e.g., North China Plain, with high concentrations of inorganic nitrate and NOx. Here we developed a method for estimation of pON from the measurements of high-resolution aerosol mass spectrometer coupled with a thermodenuder based on the volatility differences between inorganic nitrate and pON. The results generally correlated well with those estimated from positive matrix factorization of combined organic and inorganic mass spectra and from the ratio of NO+ to NO2+ (NOx+ ratio), yet they had improvements in reducing negative values due to the influences of high concentration of inorganic nitrate and constant NOx+ ratio of organic nitrates (RON). By applying this approach to the measurements at an urban (Beijing) and a rural site (Gucheng) in summer and winter in the North China Plain, we estimated that the average mass concentrations of NO3,org (1.8 µg m−3 vs. 1.0 µg m−3) and pON to OA (27.5 % vs. 14.8 %) were higher in summer than in winter in Beijing, indicating more pON formation in biogenically and anthropogenically mixed environments. In addition, the average NO3,org loading in Gucheng was 1.9 µg m−3, and the pON at the rural site also showed higher contribution to OA than that in Beijing during wintertime due to higher primary emissions and gaseous precursors in Gucheng. In addition, RON was determined and showed considerable differences between day–night and clean–polluted periods, highlighting the complexity of pON compounds from different chemical pathways (e.g., OH and NO3 oxidation) and sources.
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Xue, L. K., T. Wang, J. Gao, A. J. Ding, X. H. Zhou, D. R. Blake, X. F. Wang, et al. "Ground-level ozone in four Chinese cities: precursors, regional transport and heterogeneous processes." Atmospheric Chemistry and Physics Discussions 14, no. 14 (August 12, 2014): 20767–803. http://dx.doi.org/10.5194/acpd-14-20767-2014.
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Abstract. We analyzed measurements of ozone (O3) and its precursors made at rural/suburban sites downwind of four large Chinese cities – Beijing, Shanghai, Guangzhou and Lanzhou, to elucidate their pollution characteristics, regional transport, in situ production, and impacts of heterogeneous processes. The same measurement techniques and observation-based model were used to minimize uncertainties in comparison of the results due to difference in methodologies. All four cities suffered from serious O3 pollution but showed different precursor distributions. The model-calculated in situ O3 production rates were compared with the observed change rates to infer the relative contributions of on-site photochemistry and transport. At the rural site of Beijing, export of the well-processed urban plumes contributed to the extremely high O3 levels (up to an hourly value of 286 ppbv), while the O3 pollution observed at suburban sites of Shanghai, Guangzhou and Lanzhou was dominated by intense in-situ production. The O3 production was in a VOCs-limited regime in both Shanghai and Guangzhou, and a NOx-controlled regime in Lanzhou. The key VOC precursors are aromatics and alkenes in Shanghai, and aromatics in Guangzhou. The potential impacts on O3 production of several heterogeneous processes, namely, hydrolysis of dinitrogen pentoxide (N2O5), uptake of hydro peroxy radical (HO2) on particles and surface reactions of NO2 forming nitrous acid (HONO), were assessed. The analyses indicate the varying and considerable impacts of these processes in different areas of China depending on the atmospheric abundances of aerosol and NOx, and suggest the urgent need to better understand these processes and represent them in photochemical models.
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Tie, X., G. Brasseur, and Z. Ying. "Impact of model resolution on chemical ozone formation in Mexico City; application of the WRF-Chem model." Atmospheric Chemistry and Physics Discussions 10, no. 4 (April 16, 2010): 9801–38. http://dx.doi.org/10.5194/acpd-10-9801-2010.
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Abstract. The resolution of regional chemical/dynamical models has important effects on the calculation of distributions of air pollutants in large cities. In this study, the sensitivity of air pollutants and photochemical O3 production to different model resolutions is studied by using a regional chemical/dynamical model (version 3 of Weather Research and Forecasting Chemical model – WRF-Chemv3) in Mexico City. The model results with 3, 6, 12, and 24 km resolutions are compared to the surface measurements for CO, NOx, and O3. The study shows that the model resolutions with 3 and 6 km have reasonable simulations of surface CO, NOx, and O3 concentrations and diurnal variations. The model results intend to underestimate the measurements when the resolution is reduced to 12 km. The calculated surface CO, NOx, and O3 concentrations significantly underestimate the measured values at 24 km resolution. This study suggests that 12 km is a threshold resolution for the O3 and O3 precursor calculations for using a regional chemical/dynamical model in Mexico City. 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 with different model resolutions, (2) the emission spatial distribution of ozone precursors, and (3) the non-linearly O3 photochemical productions with different resolutions. Model studies suggest that model resolution (resulting in different meteorological condition and transport process) have larger impacts than emission inventory resolutions for the calculations of O3 and O3 precursors. The model calculations show that with coarse resolution of emission inventory (24 km) and fine meteorological condition resolution (6 km), the calculated CO and O3 are considerably improved compared to the calculation with coarse resolution for both emission inventory and meteorological condition (24 km), suggesting that the impacts of resolution on meteorological condition and transport process are largest for the calculations of O3 and O3 precursors. The emission resolution has important effects on the calculation, but the effects are smaller than the model resolution. This study also suggests that the changes of O3 precursors at different resolutions lead to important impacts on O3 chemical formation due to the non-linear relationship between O3 formation and O3 precursors. Finally, this study suggests that with the balance between the model performance and required computation time, the 6 km resolution is an optimal resolution for the calculation of O3 and O3 precursors in Mexico City.
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Song, J., W. Lei, N. Bei, M. Zavala, B. de Foy, R. Volkamer, B. Cardenas, J. Zheng, R. Zhang, and L. T. Molina. "Ozone response to emission changes: a modeling study during the MCMA-2006/MILAGRO campaign." Atmospheric Chemistry and Physics Discussions 9, no. 6 (November 3, 2009): 23419–63. http://dx.doi.org/10.5194/acpd-9-23419-2009.
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Abstract. The sensitivity of ozone production to precursor emissions was investigated under five different meteorological conditions in the Mexico City Metropolitan Area (MCMA) during the MCMA-2006/MILAGRO field campaign using the gridded photochemical model CAMx driven by observation-nudged WRF meteorology. Precursor emissions were constrained by the comprehensive data from the field campaign and the routine ambient air quality monitoring network. Simulated plume mixing and transport were examined by comparing with measurements from the G-1 aircraft during the campaign. The observed concentrations of ozone precursors and ozone were well reproduced by the model. The effects of reducing precursor emissions on urban ozone production were performed for three representative emission control strategies. A 50% reduction in VOC emissions led to 7 to 22 ppb decrease in daily maximum ozone concentrations, while a 50% reduction in NOx emissions leads to 4 to 21 ppb increase, and 50% reductions in both NOx and VOC emission decrease the daily maximum ozone concentrations up to 10 ppb. These results along with a chemical indicator analysis using the chemical production ratios of H2O2 to HNO3 demonstrate that the MCMA urban core region is VOC-limited for all meteorological episodes, which is consistent with the results from MCMA-2003 field campaign; however the degree of the VOC-sensitivity is higher in the MCMA-2006 due to lower VOC/NOx emission ratio and VOC reactivity. Ozone formation in the surrounding mountain/rural area is mostly NOx-limited, but can be VOC-limited, and the range of the NOx-limited or VOC-limited areas depends on meteorology.
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Song, J., W. Lei, N. Bei, M. Zavala, B. de Foy, R. Volkamer, B. Cardenas, J. Zheng, R. Zhang, and L. T. Molina. "Ozone response to emission changes: a modeling study during the MCMA-2006/MILAGRO Campaign." Atmospheric Chemistry and Physics 10, no. 8 (April 26, 2010): 3827–46. http://dx.doi.org/10.5194/acp-10-3827-2010.
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Abstract. The sensitivity of ozone production to precursor emissions was investigated under five different meteorological conditions in the Mexico City Metropolitan Area (MCMA) during the MCMA-2006/MILAGRO field campaign using the gridded photochemical model CAMx driven by observation-nudged WRF meteorology. Precursor emissions were constrained by the comprehensive data from the field campaign and the routine ambient air quality monitoring network. Simulated plume mixing and transport were examined by comparing with measurements from the G-1 aircraft during the campaign. The observed concentrations of ozone precursors and ozone were reasonably well reproduced by the model. The effects of reducing precursor emissions on urban ozone production were performed for three representative emission control scenarios. A 50% reduction in VOC emissions led to 7 to 22 ppb decrease in daily maximum ozone concentrations, while a 50% reduction in NOx emissions leads to 4 to 21 ppb increase, and 50% reductions in both NOx and VOC emission decrease the daily maximum ozone concentrations up to 10 ppb. These results along with a chemical indicator analysis using the chemical production ratios of H2O2 to HNO3 demonstrate that the MCMA urban core region is VOC-limited for all meteorological episodes, which is consistent with the results from MCMA-2003 field campaign; however the degree of the VOC-sensitivity is higher during MCMA-2006 due to lower VOCs, lower VOC reactivity and moderately higher NOx emissions. Ozone formation in the surrounding mountain/rural area is mostly NOx-limited, but can be VOC-limited, and the range of the NOx-limited or VOC-limited areas depends on meteorology.
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Itahashi, Syuichi, Keiya Yumimoto, Itsushi Uno, Hiroshi Hayami, Shin-ichi Fujita, Yuepeng Pan, and Yuesi Wang. "A 15-year record (2001–2015) of the ratio of nitrate to non-sea-salt sulfate in precipitation over East Asia." Atmospheric Chemistry and Physics 18, no. 4 (February 28, 2018): 2835–52. http://dx.doi.org/10.5194/acp-18-2835-2018.
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Abstract. Acidifying species in precipitation can have severe impacts on ecosystems. The chemical composition of precipitation is directly related to the amount of precipitation; accordingly, it is difficult to identify long-term variation in chemical concentrations. The ratio of the nitrate (NO3−) to non-sea-salt sulfate (nss-SO42−) concentration in precipitation on an equivalent basis (hereinafter, Ratio) is a useful index to investigate the relative contributions of these acidifying species. To identify the long-term record of acidifying species in precipitation over East Asia, the region with the highest emissions worldwide, we compiled ground-based observations of the chemical composition of precipitation over China, Korea, and Japan from 2001 to 2015 based on the Acid Deposition Monitoring Network in East Asia (EANET). The spatial coverage was limited, but additional monitoring data for Japan, southern China, and northern China around Beijing were utilized. The period of analysis was divided into three phases: Phase I (2001–2005), Phase II (2006–2010), and Phase III (2011–2015). The behaviors of NO3− and nss-SO42− concentrations and hence the Ratio in precipitation were related to these precursors. The anthropogenic NOx and SO2 emissions and the NOx ∕ SO2 emission ratio were analyzed. Further, satellite observations of the NO2 and SO2 column density to capture the variation in emissions were applied. We found that the long-term trend in the NO3− concentration in precipitation was not related to the variation in NOx emission and the NO2 column. In comparison, the nss-SO42− concentration in precipitation over China, Korea, and Japan was partially connected to the changes in SO2 emissions from China, but the trends were not significant. The long-term trends of Ratio over China, Korea, and Japan were nearly flat during Phase I, increased significantly during Phase II, and were essentially flat again during Phase III. This variation in Ratio in East Asia clearly corresponded to the NOx ∕ SO2 emission ratio and the NO2 ∕ SO2 column ratio in China. The initial flat trend during Phase I was due to increases in both NOx and SO2 emissions in China, the significantly increasing trend during Phase II was triggered by the increase in NOx emissions and decrease in SO2 emissions in China, and the return to a flat trend during Phase III was caused by declines in both NOx and SO2 emissions in China. These results suggest that emissions in China had a significant impact not only on China but also on downwind precipitation chemistry during the 15-year period of 2001–2015. In terms of wet deposition, the NO3− wet deposition over China, Korea, and Japan did not change dramatically, but the nss-SO42− wet deposition declined over China, Korea, and Japan from Phase II to III. These declines were caused by a strong decrease in the nss-SO42− concentration in precipitation accompanied by a reduction in SO2 emission from China, which counteracted the increase in precipitation. These findings indicated that the acidity of precipitation shifted from sulfur to nitrogen.
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Zhang, Kun, Zhiqiang Liu, Xiaojuan Zhang, Qing Li, Andrew Jensen, Wen Tan, Ling Huang, Yangjun Wang, Joost de Gouw, and Li Li. "Insights into the significant increase in ozone during COVID-19 in a typical urban city of China." Atmospheric Chemistry and Physics 22, no. 7 (April 12, 2022): 4853–66. http://dx.doi.org/10.5194/acp-22-4853-2022.
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Abstract. The outbreak of COVID-19 promoted strict restrictions to human activities in China, which led to a dramatic decrease in most air pollutant concentrations (e.g., PM2.5, PM10, NOx, SO2 and CO). However, an obvious increase in ozone (O3) concentrations was found during the lockdown period in most urban areas of China. In this study, we conducted field measurements targeting ozone and its key precursors by utilizing a novel proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) in Changzhou, which is representative of the Yangtze River Delta (YRD) city cluster of China. We further applied the integrated methodology including machine learning, an observation-based model (OBM) and sensitivity analysis to obtain insights into the reasons causing the obvious increase in ozone. Major findings include the following: (1) by deweathered calculation, we found changes in precursor emissions contributed 1.46 ppbv to the increase in the observed O3 during the full-lockdown period in 2020, while meteorology constrained 3.0 ppbv of O3 in the full-lockdown period of 2019. (2) By using an OBM, we found that although a significant reduction in O3 precursors was observed during the full-lockdown period, the photochemical formation of O3 was stronger than that during the pre-lockdown period. (3) The NOx/VOC ratio dropped dramatically from 1.84 during the pre-lockdown to 0.79 in the full-lockdown period, which switched O3 formation from a VOC-limited regime to the boundary of a NOx- and VOC-limited regime. Additionally, box model results suggested that the decrease in the NOx/VOC ratio during the full-lockdown period could increase the mean O3 by 2.4 ppbv. Results of this study give insights into the relationship between O3 and its precursors in urban area and demonstrate reasons for the obvious increase in O3 in most urban areas of China during the COVID-19 lockdown period. This study also underlines the necessity of controlling anthropogenic oxygenated volatile organic compounds (OVOCs), alkenes and aromatics in the sustained campaign of reducing O3 pollution in China.
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Kim, Dongjin, Wonbae Jeon, Jaehyeong Park, Jeonghyeok Mun, Hyunsik Choi, Cheol-Hee Kim, Hyo-Jung Lee, and Hyun-Young Jo. "A Numerical Analysis of the Changes in O3 Concentration in a Wildfire Plume." Remote Sensing 14, no. 18 (September 12, 2022): 4549. http://dx.doi.org/10.3390/rs14184549.
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This study analyzed the characteristics of changes in O3 concentration in a plume induced by a wildfire in Andong, South Korea, from 24 to 26 April 2020, using the Community Multi-scale Air Quality (CMAQ) model. Fire INventory from National Center for Atmospheric Research (FINN) emissions data were used for the wildfire emissions. The increases in the concentrations of primary pollutants (CO, NOx, and volatile organic compounds (VOCs)) due to the wildfire peaked near the source at 09 LST and, as the plume was transported, the reduction in the supply of pollutants from wildfire, as well as chemical reactions, advection and diffusion, and deposition, caused the concentrations to continuously decrease. In contrast, O3 concentration showed a sustained increase during transport due to photochemical reactions caused by precursors (e.g., NOx, VOCs) emitted during the wildfire, peaking (1.40 ppb) at approximately 1 km at 13 LST over 60 km from the source. To analyze these results, a process analysis was conducted. Integrated process rate (IPR) analysis results showed that the production rate of O3 and loss rates of NOx and VOCs peaked at 09 LST due to the photochemical reactions of NOx and VOCs emitted due to wildfire. Then, as the plume was transported, the loss rates of NOx and VOCs that contributed to O3 production continued to decrease at 11 LST. The O3 production rate also decreased at 11 LST but increased at 13 LST due to increasing solar radiation. This indicates that the O3 concentration is complexly determined by O3 precursors and solar radiation. Additionally, IRR analysis revealed that NO and NO2 emitted during wildfire and solar radiation contributed to the production and loss processes of O3; the production reactions of O3 were predominant, and O3 was accumulated and transported in the plume, leading to the peak O3 concentration at 13 LST.
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Lei, W., B. de Foy, M. Zavala, R. Volkamer, and L. T. Molina. "Characterizing ozone production in the Mexico City Metropolitan Area: a case study using a chemical transport model." Atmospheric Chemistry and Physics 7, no. 5 (February 27, 2007): 1347–66. http://dx.doi.org/10.5194/acp-7-1347-2007.
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Abstract. An episodic simulation is conducted to characterize midday (12:00–17:00 CDT) ozone (O3) photochemical production and to investigate its sensitivity to emission changes of ozone precursors in the Mexico City Metropolitan Area (MCMA) during an "O3-South" meteorological episode using the Comprehensive Air Quality Model with extensions (CAMx). High Ox (O3+NO2) photochemical production rates of 10–80 ppb/h are predicted due to the high reactivity of volatile organic compounds (VOCs) in which alkanes, alkenes, and aromatics exert comparable contributions. The predicted ozone production efficiency is between 4–10 O3 molecules per NOx molecule oxidized, and increases with VOC-to-NO2 reactivity ratio. Process apportionment analyses indicate significant outflow of pollutants such as O3 and peroxyacetyl nitrate (PAN) from the urban area to the surrounding regional environment. PAN is not in chemical-thermal equilibrium during the photochemically active periods. Sensitivity studies of O3 production suggest that O3 formation in the MCMA urban region with less chemical aging (NOz/NOy<0.3) is VOC-limited. Both the simulated behavior of O3 production and its sensitivities to precursors suggest that midday O3 formation during this episode is VOC-sensitive in the urban region on the basis of the current emissions inventory estimates, and current NOx levels depress the O3 production.
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Lei, H., and J. X. L. Wang. "Sensitivities of NO<sub>x</sub> transformation and the effects on surface ozone and nitrate." Atmospheric Chemistry and Physics Discussions 13, no. 8 (August 23, 2013): 21961–88. http://dx.doi.org/10.5194/acpd-13-21961-2013.
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Abstract. As precursors for tropospheric ozone and nitrate aerosols, Nitrogen oxides (NOx) in present atmosphere and its transformation in responding to emission and climate perturbations are studied by CAM-Chem model and air quality measurements including National Emission Inventory (NEI), Clean Air Status and Trends Network (CASTNET) and Environmental Protection Agency Air Quality System (EPA AQS). It is found that not only the surface ozone formation but also the nitrate formation is associated with the relative emissions of NOx and volatile organic compounds (VOC). Due to the availability of VOC and associated NOx titration, ozone productions in industrial regions increase in warmer conditions and slightly decrease against NOx emission increase, which is converse to the response in farming region. The decrease or small increase in ozone concentrations over industrial regions result in the responded nitrate increasing rate staying above the increasing rate of NOx emissions. It is indicated that ozone concentration change is more directly affected by changes in climate and precursor emissions, while nitrate concentration change is also affected by local ozone production types and their seasonal transfer. The sensitivity to temperature perturbations shows that warmer climate accelerates the decomposition of odd nitrogen (NOy) during the night. As a result, the transformation rate of NOx to nitrate decreases. Examinations on the historical emission and air quality records on typical pollution areas further confirm the conclusion drawn from modeling experiments.
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Xue, L. K., T. Wang, J. Gao, A. J. Ding, X. H. Zhou, D. R. Blake, X. F. Wang, et al. "Ground-level ozone in four Chinese cities: precursors, regional transport and heterogeneous processes." Atmospheric Chemistry and Physics 14, no. 23 (December 10, 2014): 13175–88. http://dx.doi.org/10.5194/acp-14-13175-2014.
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Abstract. We analyzed the measurements of ozone (O3) and its precursors made at rural/suburban sites downwind of four large Chinese cities – Beijing, Shanghai, Guangzhou and Lanzhou, to elucidate their pollution characteristics, regional transport, in situ production, and impacts of heterogeneous processes. The same measurement techniques and observation-based model were used to minimize uncertainties in comparison of the results due to difference in methodologies. All four cities suffered from serious O3 pollution but showed different precursor distributions. The model-calculated in situ O3 production rates were compared with the observed change rates to infer the relative contributions of on-site photochemistry and transport. At the rural site downwind of Beijing, export of the well-processed urban plumes contributed to the extremely high O3 levels (up to an hourly value of 286 ppbv), while the O3 pollution observed at suburban sites of Shanghai, Guangzhou and Lanzhou was dominated by intense in situ production. The O3 production was in a volatile organic compound (VOC)-limited regime in both Shanghai and Guangzhou, and a NOx-limited regime in Lanzhou. The key VOC precursors are aromatics and alkenes in Shanghai, and aromatics in Guangzhou. The potential impacts on O3 production of several heterogeneous processes, namely, hydrolysis of dinitrogen pentoxide (N2O5), uptake of hydro peroxy radical (HO2) on particles and surface reactions of NO2 forming nitrous acid (HONO), were assessed. The analyses indicate the varying and considerable impacts of these processes in different areas of China depending on the atmospheric abundances of aerosol and NOx, and suggest the urgent need to better understand these processes and represent them in photochemical models.
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LaFranchi, B. W., G. M. Wolfe, J. A. Thornton, S. A. Harrold, E. C. Browne, K. E. Min, P. J. Wooldridge, et al. "Closing the peroxy acetyl (PA) radical budget: observations of acyl peroxy nitrates (PAN, PPN, and MPAN) during BEARPEX 2007." Atmospheric Chemistry and Physics Discussions 9, no. 2 (April 20, 2009): 9879–926. http://dx.doi.org/10.5194/acpd-9-9879-2009.
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Abstract. Acyl peroxy nitrates (APNs, also known as PANs) are formed from the oxidation of aldehydes and other oxygenated VOC (oVOC) in the presence of NO2. Formation of APNs suppresses NOx (NOx≡NO+NO2) in urban areas and enhances NOx downwind in urban plumes, increasing the rate of ozone production throughout an urban plume. APNs also redistribute NOx on global scales, enhancing NOx and thus ozone production. There are both anthropogenic and biogenic oVOC precursors to APNs, but a detailed evaluation of their chemistry against observations has proven elusive. Here we describe measurements of PAN, PPN, and MPAN along with the majority of chemicals that participate in their production and loss, including OH, HO2, numerous oVOC, and NO2. Observations were made during the Biosphere Effects on AeRosols and Photochemistry Experiment (BEARPEX 2007) in the outflow of the Sacramento urban plume. These observations are used to evaluate a detailed chemical model of APN ratios and concentrations. We find the ratios of APNs are nearly independent of the loss mechanisms and thus an especially good test of our understanding of their sources. We show that oxidation of methylvinyl ketone, methacrolein, methyl glyoxal, biacetyl and acetaldehyde are all significant sources of the PAN+peroxy acetyl (PA) radical reservoir, with methylvinyl ketone (MVK) often being the primary non-acetaldehyde source. At high temperatures, oxidation of non-acetaldehyde PA radical sources contributes over 60% to the total PA production rate. An analysis of absolute APN concentrations reveals a missing APN sink that can be resolved by increasing the PA+∑RO2 rate constant by a factor of 3.
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Murphy, J. G., D. A. Day, P. A. Cleary, P. J. Wooldridge, D. B. Millet, A. H. Goldstein, and R. C. Cohen. "The weekend effect within and downwind of Sacramento: Part 2. Observational evidence for chemical and dynamical contributions." Atmospheric Chemistry and Physics Discussions 6, no. 6 (November 24, 2006): 11971–2019. http://dx.doi.org/10.5194/acpd-6-11971-2006.
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Abstract. Observations of day-of-week patterns and diurnal profiles of ozone, volatile organic compounds and nitrogen oxides are examined to assess the chemical and dynamical factors governing the daytime ozone accumulation and the distribution of chemically related species in Central California. Isoprene observations show that urban OH concentrations are higher on the weekend whereas rural OH concentrations are lower on the weekend, confirming that NOx concentrations have a direct effect on the rate of photochemical ozone production and that the transition from NOx-saturated (VOC-limited) to NOx-limited chemistry occurs between the city and the downwind rural counties. We quantify the extent to which mixing of ozone and its precursors from aloft contributes to the daytime accumulation of ozone at the surface in Sacramento. Ozone production in the rural Mountain Counties is currently NOx-limited and will decrease in response to NOx emission reductions in the Sacramento Valley. However, NOx emissions reductions of at least 50% (from weekday levels) are necessary to bring about a significant decrease in accumulation of ozone at the surface in the Sacramento Valley. The impact of NOx emission reductions on the frequency of exceeding the federal 8-hour ozone standard at an individual site will depend on the balance between reduced titration and the sign and magnitude of production changes. We further show that HNO3 production, which depends on the product of OH and NO2 mixing ratios, is a constant at high NOx, suggesting that NOx must be reduced below a threshold before nitrate aerosol can be expected to decrease.
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Huang, Yaoxian, Shiliang Wu, Louisa J. Kramer, Detlev Helmig, and Richard E. Honrath. "Surface ozone and its precursors at Summit, Greenland: comparison between observations and model simulations." Atmospheric Chemistry and Physics 17, no. 23 (December 8, 2017): 14661–74. http://dx.doi.org/10.5194/acp-17-14661-2017.
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Abstract. Recent studies have shown significant challenges for atmospheric models to simulate tropospheric ozone (O3) and its precursors in the Arctic. In this study, ground-based data were combined with a global 3-D chemical transport model (GEOS-Chem) to examine the abundance and seasonal variations of O3 and its precursors at Summit, Greenland (72.34° N, 38.29° W; 3212 m a.s.l.). Model simulations for atmospheric nitrogen oxides (NOx), peroxyacetyl nitrate (PAN), ethane (C2H6), propane (C3H8), carbon monoxide (CO), and O3 for the period July 2008–June 2010 were compared with observations. The model performed well in simulating certain species (such as CO and C3H8), but some significant discrepancies were identified for other species and further investigated. The model generally underestimated NOx and PAN (by ∼ 50 and 30 %, respectively) for March–June. Likely contributing factors to the low bias include missing NOx and PAN emissions from snowpack chemistry in the model. At the same time, the model overestimated NOx mixing ratios by more than a factor of 2 in wintertime, with episodic NOx mixing ratios up to 15 times higher than the typical NOx levels at Summit. Further investigation showed that these simulated episodic NOx spikes were always associated with transport events from Europe, but the exact cause remained unclear. The model systematically overestimated C2H6 mixing ratios by approximately 20 % relative to observations. This discrepancy can be resolved by decreasing anthropogenic C2H6 emissions over Asia and the US by ∼ 20 %, from 5.4 to 4.4 Tg year−1. GEOS-Chem was able to reproduce the seasonal variability of O3 and its spring maximum. However, compared with observations, it underestimated surface O3 by approximately 13 % (6.5 ppbv) from April to July. This low bias appeared to be driven by several factors including missing snowpack emissions of NOx and nitrous acid in the model, the weak simulated stratosphere-to-troposphere exchange flux of O3 over the summit, and the coarse model resolution.
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Liu, Qi Dong, Su Ping Cui, Hong Xia Guo, Ya Li Wang, and Yun Feng Zhang. "Preparation and Characterization of MnOX-CeO2/TiO2 Catalytic Material for SCR of NOX with NH3 at Low Temperature." Materials Science Forum 743-744 (January 2013): 198–203. http://dx.doi.org/10.4028/www.scientific.net/msf.743-744.198.
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The MnOX-CeO2/TiO2 catalytic material for low temperature SCR of NOX with NH3 was prepared using aqueous solutions of three manganese salt as well as cerous nitrate and TiO2(anatase) powder by impregnation method. The properties of the catalytic materials were investigated by TG-DSC, XRF, XRD, XPS, BET and SEM. And the low temperature catalytic activity of the catalytic materials was measured. The results showed that, when manganese nitrate and manganese chloride and manganese acetate were used as precursors, respectively, the primary phases of catalytic materials were MnOx/MnO2, MnO2/Mn8O10Cl3 and Mn3O4/MnO2, the surface Mn/Ti molar ratio were 0.68, 0.19 and 0.88, the surface area were 45.1m2/g, 25.1 m2/g and 48.6 m2/g ,respectively. The optimum NOX conversion rate of catalytic material from manganese nitrate precursor and manganese chloride precursor and manganese acetate precursor were 97.9% at 483K, 86.6% at 513K, 97.2% at 423K, respectively. Consequently, the higher low-temperature activity of MnOX-CeO2/TiO2 from manganese acetate precursor may be attributed to higher surface and higher surface concentration of activity component.
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Chang, C. C., M. Shao, C. C. K. Chou, S. C. Liu, J. L. Wang, K. Z. Lee, C. H. Lai, T. Zhu, and P. H. Lin. "Biogenic isoprene and implications for oxidant levels in Beijing during the 2008 Olympic Games." Atmospheric Chemistry and Physics Discussions 13, no. 10 (October 9, 2013): 25939–67. http://dx.doi.org/10.5194/acpd-13-25939-2013.
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Abstract. As the host of the 2008 Summer Olympic Games, Beijing implemented a series of stringent, short-term air quality control measures to reduce the emissions of anthropogenic air pollutants. Large reductions in the daily average concentrations of primary pollutants, e.g., non-methane hydrocarbons (NMHCs) and nitrogen oxides (NOx) of approximately 50% were observed at the air quality observatory of Peking University. Nevertheless, high levels of ozone were present during the control period. Although anthropogenic precursors were greatly reduced, the meteorological conditions in summer, including high temperature and light flux, are conducive to the production of large amounts of biogenic isoprene, which is extremely reactive. The diurnal pattern of isoprene showed daily maximum mixing ratios of 0.83 ppbv at noon and a minimum at night, reflecting its primarily biogenic properties. Using the ratio of isoprene to vehicle exhaust tracers, approximately 92% of the daytime isoprene was estimated from biogenic sources, and only 8% was attributed to vehicular emissions. In terms of OH reactivity and the ozone formation potential (OFP), biogenic isoprene with its midday surge can contribute approximately 20% of the total OFPs and 40–50% of the total OH reactivities of the 65 measured NMHCs during the midday hours. The discrepancy between decreased precursor levels and the observed high ozone was most likely caused by a combination of many factors. The changes in the partition among the components of oxidation products (O3, NO2 and NOz) and the contribution of air pollutants from regional sources outside Beijing should be two primary reasons. Furthermore, the influences of biogenic isoprene as well as the non-linearity of O3-VOC-NOx chemistry are other major concerns that can reduce the effectiveness of the control measures for decreasing ozone formation. Although anthropogenic precursors were greatly reduced during the Olympic Games, sufficient biogenic isoprene and moderate NOx were still present in the conditions of high radiation flux and temperature during midday and early afternoon, which can still contribute a significant fraction of midday and early afternoon O3.
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von Schneidemesser, E., M. Vieno, and P. S. Monks. "The changing oxidizing environment in London – trends in ozone precursors and their contribution to ozone production." Atmospheric Chemistry and Physics Discussions 14, no. 2 (January 16, 2014): 1287–316. http://dx.doi.org/10.5194/acpd-14-1287-2014.
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Abstract. Ground-level ozone is recognized to be a threat to human health (WHO, 2003), have a deleterious impact on vegetation (Fowler et al., 2009), is also an important greenhouse gas (IPCC, 2007) and key to the oxidative ability of the atmosphere (Monks et al., 2009). Owing to its harmful effect on health, much policy and mitigation effort has been put into reducing its precursors – the nitrogen oxides (NOx) and non-methane volatile organic compounds (NMVOCs). The non-linear chemistry of tropospheric ozone formation, dependent mainly on NOx and NMVOC concentrations in the atmosphere, makes controlling tropospheric ozone complex. Furthermore, the concentration of ozone at any given point is a complex superimposition of in-situ produced or destroyed ozone and transported ozone on the regional and hemispheric-scale. In order to effectively address ozone, a more detailed understanding of its origins is needed. Here we show that roughly half (5 μg m−3) of the observed increase in urban (London) ozone (10 μg m−3) in the UK from 1998 to 2008 is owing to factors of local origin, in particular, the change in NO : NO2 ratio, NMVOC : NOx balance, NMVOC speciation, and emission reductions (including NOx titration). In areas with previously higher large concentrations of nitrogen oxides, ozone that was previously suppressed by high concentrations of NO has now been "unmasked", as in London and other urban areas of the UK. The remaining half (approximately 5 μg m−3) of the observed ozone increase is attributed to non-local factors such as long-term transport of ozone, changes in background ozone, and meteorological variability. These results show that a two-pronged approach, local action and regional-to-hemispheric cooperation, is needed to reduce ozone and thereby population exposure, which is especially important for urban ozone.
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Yang, Laura Hyesung, Daniel J. Jacob, Ruijun Dang, Yujin J. Oak, Haipeng Lin, Jhoon Kim, Shixian Zhai, et al. "Interpreting Geostationary Environment Monitoring Spectrometer (GEMS) geostationary satellite observations of the diurnal variation in nitrogen dioxide (NO2) over East Asia." Atmospheric Chemistry and Physics 24, no. 12 (June 18, 2024): 7027–39. http://dx.doi.org/10.5194/acp-24-7027-2024.
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Abstract. Nitrogen oxide radicals (NOx≡NO+NO2) emitted by fuel combustion are important precursors of ozone and particulate matter pollution, and NO2 itself is harmful to public health. The Geostationary Environment Monitoring Spectrometer (GEMS), launched in space in 2020, now provides hourly daytime observations of NO2 columns over East Asia. This diurnal variation offers unique information on the emission and chemistry of NOx, but it needs to be carefully interpreted. Here we investigate the drivers of the diurnal variation in NO2 observed by GEMS during winter and summer over Beijing and Seoul. We place the GEMS observations in the context of ground-based column observations (Pandora instruments) and GEOS-Chem chemical transport model simulations. We find good agreement between the diurnal variations in NO2 columns in GEMS, Pandora, and GEOS-Chem, and we use GEOS-Chem to interpret these variations. NOx emissions are 4 times higher in the daytime than at night, driving an accumulation of NO2 over the course of the day, offset by losses from chemistry and transport (horizontal flux divergence). For the urban core, where the Pandora instruments are located, we find that NO2 in winter increases throughout the day due to high daytime emissions and increasing NO2/NOx ratio from entrainment of ozone, partly balanced by loss from transport and with a negligible role of chemistry. In summer, by contrast, chemical loss combined with transport drives a minimum in the NO2 column at 13:00–14:00 local time (LT). Segregation of the GEMS data by wind speed further demonstrates the effect of transport, with NO2 in winter accumulating throughout the day at low winds but flat at high winds. The effect of transport can be minimized in summer by spatially averaging observations over the broader metropolitan scale, under which conditions the diurnal variation in NO2 reflects a dynamic balance between emission and chemical loss.
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Kramer, L. J., D. Helmig, J. F. Burkhart, A. Stohl, S. Oltmans, and R. E. Honrath. "Seasonal variability of atmospheric nitrogen oxides and non-methane hydrocarbons at the GEOSummit station, Greenland." Atmospheric Chemistry and Physics Discussions 14, no. 9 (May 27, 2014): 13817–67. http://dx.doi.org/10.5194/acpd-14-13817-2014.
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Abstract. Measurements of atmospheric NOx (NOx = NO + NO2), peroxyacetyl nitrate (PAN), NOy and non-methane hydrocarbons (NMHC) were taken at the GEOSummit Station, Greenland (72.34° N, 38.29° W, 3212 m.a.s.l) from July 2008 to July 2010. The data set represents the first year-round concurrent record of these compounds sampled at a high latitude Arctic site in the free troposphere. Here, the study focused on the seasonal variability of these important ozone (O3) precursors in the Arctic free troposphere and the impact from transported anthropogenic and biomass burning emissions. Our analysis shows that PAN is the dominant NOy species in all seasons at Summit, varying from 49% to 78%, however, we find that odd NOy species (odd NOy = NOy − PAN-NOx) contribute a large amount to the total NOy speciation with monthly means of up to 95 pmol mol−1 in the winter and ∼40 pmol mol−1 in the summer, and that the level of odd NOy species at Summit during summer is greater than that of NOx. We hypothesize that the source of this odd NOy is most likely alkyl nitrates from transported pollution, and photochemically produced species such as HNO3 and HONO. FLEXPART retroplume analysis and tracers for anthropogenic and biomass burning emissions, were used to identify periods when the site was impacted by polluted air masses. Europe contributed the largest source of anthropogenic emissions during the winter and spring months, with up to 82% of the simulated anthropogenic black carbon originating from this region between December 2009 and March 2010, whereas, North America was the primary source of biomass burning emissions. Polluted air masses were typically aged, with median transport times to the site from the source region of 11 days for anthropogenic events in winter, and 14 days for BB plumes. Overall we find that the transport of polluted air masses to the high altitude Arctic typically resulted in high variability in levels of O3 and O3 precursors. During winter, plumes originating from mid-latitude regions and transported in the lower troposphere to Summit often result in lower O3 mole fractions than background levels. However, plumes transported at higher altitudes can result in positive enhancements in O3 levels. It is therefore likely that the air masses transported in the mid-troposphere were mixed with air from stratospheric origin. Similar enhancements in O3 and its precursors were also observed during periods when FLEXPART indicated that biomass burning emissions impacted Summit. The analysis of anthropogenic events over summer show that emissions of anthropogenic origin have a greater impact on O3 and precursor levels at Summit than biomass burning sources during the measurement period, with enhancements above background levels of up to 16 nmol mol−1 for O3 and 237 pmol mol−1 and 205 pmol mol−1, 28 pmol mol−1 and 1.0 nmol mol−1 for NOy, PAN, NOx and ethane, respectively.
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Doherty, R. M., D. S. Stevenson, W. J. Collins, and M. G. Sanderson. "Influence of convective transport on tropospheric ozone and its precursors in a chemistry-climate model." Atmospheric Chemistry and Physics Discussions 5, no. 3 (June 7, 2005): 3747–71. http://dx.doi.org/10.5194/acpd-5-3747-2005.
Full textAbstract:
Abstract. The impact of convection on tropospheric O3 and its precursors has been examined in a coupled chemistry-climate model. There are two ways that convection affects O3. First, convection affects O3 by vertical mixing of O3 itself. Convection lifts lower tropospheric air to regions where the ozone lifetime is longer, whilst mass-balance subsidence mixes O3-rich upper tropospheric (UT) air downwards to regions where the O3 lifetime is shorter. This tends to decrease UT ozone and the overall tropospheric column of O3. Secondly, convection affects O3 by vertical mixing of ozone precursors. This affects O3 chemical production and destruction. Convection transports isoprene and its degradation products to the UT where they interact with lightning NOx to produce PAN, at the expense of NOx. The combined effect of NOx to PAN conversions and downward transport of lightning NOx results in UT NOx decreases. Convective lofting of NOx from surface sources appears relatively unimportant. Despite UT NOx decreases, UT O3 production increases as a result of UT HOx increases driven by isoprene oxidation chemistry. However, UT O3 tends to decrease, as the effect of convective overturning of O3 itself dominates over changes in O3 chemistry. The changes in tropical UT O3 are transported polewards resulting in a 15% decrease in the global tropospheric O3 burden. These results contrast with an earlier study that uses a model of similar chemical complexity. Differences in chemistry schemes - in particular isoprene-driven changes, as well as differences in convection schemes themselves, are the most likely causes of such discrepancies. Further modelling studies are needed to constrain this uncertainty range.
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Silva, Rafaela C. V., and José C. M. Pires. "Surface Ozone Pollution: Trends, Meteorological Influences, and Chemical Precursors in Portugal." Sustainability 14, no. 4 (February 19, 2022): 2383. http://dx.doi.org/10.3390/su14042383.
Full textAbstract:
Surface ozone (O3) is a secondary air pollutant, harmful to human health and vegetation. To provide a long-term study of O3 concentrations in Portugal (study period: 2009–2019), a statistical analysis of ozone trends in rural stations (where the highest concentrations can be found) was first performed. Additionally, the effect of nitrogen oxides (NOx) and meteorological variables on O3 concentrations were evaluated in different environments in northern Portugal. A decreasing trend of O3 concentrations was observed in almost all monitoring stations. However, several exceedances to the standard values legislated for human health and vegetation protection were recorded. Daily and seasonal O3 profiles showed high concentrations in the afternoon and summer (for all inland rural stations) or spring (for Portuguese islands). The high number of groups obtained from the cluster analysis showed the difference of ozone behaviour amongst the existent rural stations, highlighting the effectiveness of the current geographical distribution of monitoring stations. Stronger correlations between O3, NO, and NO2 were detected at the urban site, indicating that the O3 concentration was more NOx-sensitive in urban environments. Solar radiation showed a higher correlation with O3 concentration regarding the meteorological influence. The wind and pollutants transport must also be considered in air quality studies. The presented results enable the definition of air quality policies to prevent and/or mitigate unfavourable outcomes from O3 pollution.