scholarly journals Contributions to OH reactivity from unexplored volatile organic compounds measured by PTR-ToF-MS – a case study in a suburban forest of the Seoul metropolitan area during the Korea–United States Air Quality Study (KORUS-AQ) 2016

2021 ◽  
Vol 21 (8) ◽  
pp. 6331-6345
Author(s):  
Dianne Sanchez ◽  
Roger Seco ◽  
Dasa Gu ◽  
Alex Guenther ◽  
John Mak ◽  
...  

Abstract. We report OH reactivity observations by a chemical ionization mass spectrometer–comparative reactivity method (CIMS-CRM) instrument in a suburban forest of the Seoul metropolitan area (SMA) during the Korea–United States Air Quality Study (KORUS-AQ 2016) from mid-May to mid-June of 2016. A comprehensive observational suite was deployed to quantify reactive trace gases inside of the forest canopy including a high-resolution proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). An average OH reactivity of 30.7±5.1 s−1 was observed, while the OH reactivity calculated from CO, NO+NO2 (NOx), ozone (O3), sulfur dioxide (SO2), and 14 volatile organic compounds (VOCs) was 11.8±1.0 s−1. An analysis of 346 peaks from the PTR-ToF-MS accounted for an additional 6.0±2.2 s−1 of the total measured OH reactivity, leaving 42.0 % missing OH reactivity. A series of analyses indicate that the missing OH reactivity most likely comes from VOC oxidation products of both biogenic and anthropogenic origin.

2020 ◽  
Author(s):  
Dianne Sanchez ◽  
Roger Seco ◽  
Dasa Gu ◽  
Alex Guenther ◽  
John Mak ◽  
...  

Abstract. We report OH reactivity observations by a chemical ionization mass spectrometer – comparative reactivity method (CIMS-CRM) instrument in a suburban forest of the Seoul Metropolitan Area (SMA) during Korea US Air Quality Study (KORUS-AQ 2016) from mid-May to mid-June of 2016. A comprehensive observational suite was deployed to quantify reactive trace gases inside of the forest canopy including a high-resolution proton transfer reaction time of flight mass spectrometer (PTR-ToF-MS). An average OH reactivity of 30.7 ± 5.1 s−1 was observed, while the OH reactivity calculated from CO, NO + NO2 (NOx), ozone (O3), sulfur dioxide (SO2), and 14 volatile organic compounds (VOCs) was 11.8 ± 1.0 s−1. An analysis of 346 peaks from the PTR-ToF-MS accounted for an additional 6.0 ± 2.2 s−1 of the total measured OH reactivity, leaving 42.0 % missing OH reactivity. The missing OH reactivity most likely comes from VOC oxidation products of both biogenic and anthropogenic origin.


2020 ◽  
Vol 20 (23) ◽  
pp. 14769-14785
Author(s):  
Caihong Wu ◽  
Chaomin Wang ◽  
Sihang Wang ◽  
Wenjie Wang ◽  
Bin Yuan ◽  
...  

Abstract. Volatile organic compounds (VOCs) play important roles in the tropospheric atmosphere. In this study, VOCs were measured at an urban site in Guangzhou, one of the megacities in the Pearl River Delta (PRD), using a gas chromatograph–mass spectrometer/flame ionization detection (GC–MS/FID) and a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). Diurnal profile analyses show that stronger chemical removal by OH radicals for more reactive hydrocarbons occurs during the daytime, which is used to estimate the daytime average OH radical concentration. In comparison, diurnal profiles of oxygenated volatile organic compounds (OVOCs) indicate evidence of contributions from secondary formation. Detailed source analyses of OVOCs, using a photochemical age-based parameterization method, suggest important contributions from both primary emissions and secondary formation for measured OVOCs. During the campaign, around 1700 ions were detected in PTR-ToF-MS mass spectra, among which there were 462 ions with noticeable concentrations. VOC signals from these ions are quantified based on the sensitivities of available VOC species. OVOC-related ions dominated PTR-ToF-MS mass spectra, with an average contribution of 73 % ± 9 %. Combining measurements from PTR-ToF-MS and GC–MS/FID, OVOCs contribute 57 % ± 10 % to the total concentration of VOCs. Using concurrent measurements of OH reactivity, OVOCs measured by PTR-ToF-MS contribute greatly to the OH reactivity (19 % ± 10 %). In comparison, hydrocarbons account for 21 % ± 11 % of OH reactivity. Adding up the contributions from inorganic gases (48 % ± 15 %), ∼ 11 % (range of 0 %–19 %) of the OH reactivity remains `missing”, which is well within the combined uncertainties between the measured and calculated OH reactivity. Our results demonstrate the important roles of OVOCs in the emission and evolution budget of VOCs in the urban atmosphere.


Elem Sci Anth ◽  
2020 ◽  
Vol 8 ◽  
Author(s):  
Jason R. Schroeder ◽  
James H. Crawford ◽  
Joon-Young Ahn ◽  
Limseok Chang ◽  
Alan Fried ◽  
...  

The Seoul Metropolitan Area (SMA) has a population of 24 million and frequently experiences unhealthy levels of ozone (O3). In this work, measurements taken during the Korea-United States Air Quality Study (KORUS-AQ, 2016) are used to explore regional gradients in O3 and its chemical precursors, and an observationally-constrained 0-D photochemical box model is used to quantify key aspects of O3 production including its sensitivity to precursor gases. Box model performance was evaluated by comparing modeled concentrations of select secondary species to airborne measurements. These comparisons indicate that the steady state assumption used in 0-D box models cannot describe select intermediate species, highlighting the importance of having a broad suite of trace gases as model constraints. When fully constrained, aggregated statistics of modeled O3 production rates agreed with observed changes in O3, indicating that the box model was able to represent the majority of O3 chemistry. Comparison of airborne observations between urban Seoul and a downwind receptor site reveal a positive gradient in O3 coinciding with a negative gradient in NOx, no gradient in CH2O, and a slight positive gradient in modeled rates of O3 production. Together, these observations indicate a radical-limited (VOC-limited) O3 production environment in the SMA. Zero-out simulations identified C7+ aromatics as the dominant VOC contributors to O3 production, with isoprene and anthropogenic alkenes making smaller but appreciable contributions. Simulations of model sensitivity to decreases in NOx produced results that were not spatially uniform, with large increases in O3 production predicted for urban Seoul and decreases in O3 production predicted for far-outlying areas. The policy implications of this work are clear: Effective O3 mitigation strategies in the SMA must focus on reducing local emissions of C7+ aromatics, while reductions in NOx emissions may increase O3 in some areas but generally decrease the regional extent of O3 exposure.


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