Grantee Research Project Results
2022 Progress Report: Evaluating chemical mechanisms with recent field data to account for the contributions of volatile chemical product emissions to urban ozone pollution
EPA Grant Number: R840010Title: Evaluating chemical mechanisms with recent field data to account for the contributions of volatile chemical product emissions to urban ozone pollution
Investigators: Stockwell, Chelsea , Li, Meng , Coggon, Matthew , McDonald, Brian
Current Investigators: Bates, Kelvin , Li, Meng , Stockwell, Chelsea , McDonald, Brian , Coggon, Matthew , Schwantes, Rebecca
Institution: University of Colorado at Boulder , NOAA Earth System Research Laboratories
EPA Project Officer: Chung, Serena
Project Period: August 1, 2020 through July 31, 2023 (Extended to April 30, 2024)
Project Period Covered by this Report: August 1, 2021 through July 31,2022
Project Amount: $396,135
RFA: Chemical Mechanisms to Address New Challenges in Air Quality Modeling (2019) RFA Text | Recipients Lists
Research Category: Early Career Awards , Air , Air Quality and Air Toxics
Objective:
The objective of this research is to improve the representation of reactions that describe the chemical oxidation of volatile chemical product (VCP) emissions in urban air quality models. The objectives for Year 2 were to evaluate VCP emissions with field measurements from SUNVEx and RECAP-CA, use box models to search for tracers of VCP oxidation, and apply updates to chemical mechanisms to our WRF-Chem simulations to evaluate the role of VCP emissions and chemistry on simulations of ozone and other secondary compounds.
Progress Summary:
This work has analyzed recent field observations in Las Vegas and Los Angeles which included new instrumentation capable of measuring key VOC markers emitted from VCPs. Our observations confirm that glycols are an important contributor to urban VOCs, and that the FIVE- VCP inventory captures the magnitude of VCP emissions. We also observe significant contributions of cooking emissions to urban VOCs. These emissions are rich in unsaturated aldehydes and are presently underrepresented in our emissions inventories. We have identified nonanal as a tracer for cooking emissions, and we have estimated top-down VOC emissions from cooking that we have incorporated into our emissions inventories.
Based on observations of VCP, mobile source, and cooking markers, we have updated our WRF- Chem emissions inventories and incorporated source sector tracers and chemistry into a mechanism named RACM2_BERK_VCP. This mechanism is based on RACM2 and includes the updates to isoprene chemistry described by Zare et al., 2018 along with the VCP updates described in Coggon et al. 2021. This mechanism includes tracers for VCP and cooking emissions that can be used to evaluate model performance in representing VOC sources. Our preliminary analysis shows that WRF-Chem simulations of the SUNVEx and RECAP-CA datasets reproduce ground, mobile laboratory, and aircraft measurements of VCP tracers such as D5 siloxane, D4- siloxane, parachlorobenzotriflouride, paradichlorobenzene, as well as new tracers for cooking, such as nonanal. The model representation of ozone formation is also well represented, and we are conducting sensitivity analyses that will determine the impact of each sector on total ozone formation.
Finally, to complement WRF-Chem, we have built a box model that simulates the transport, emissions, and atmospheric chemistry of VOCs in the Los Angeles Basin. This model will enable us to conduct sensitivity analyses on the detailed emissions inventory used in WRF-Chem, test mechanisms with different chemical complexity, and evaluate the resulting models against our detailed chemical measurements from SUNVEx / RECAP-CA. We find that the model performs well in reproducing the observed mixing ratios of VCP, cooking, and mobile source VOC tracers at the RECAP-CA groundsite, and that the production of ozone and peroxy acyl nitrates (PANs) are within measurement uncertainty.
Future Activities:
We plan to use our measurements and updated models to quantify the impacts of VCPs and cooking on ozone and PAN production in the Los Angeles region during RECAP-CA. In WRF-Chem, we will conduct sensitivity analyses that will determine the basin-wide impacts of VCPs, mobile sources, cooking emissions, and biogenic sources on ozone production. In our box model, we will test the impact of different chemical mechanisms on the production of key secondary gasses (e.g., ozone, PAN, formaldehyde), and evaluate simulations using chemical mechanisms, such as the MCM, to interpret our detailed suite of chemical measurements.
References:
Arata, C. et al.: Volatile organic compound emissions during HOMEChem, Indoor Air, 31, 20992117, 2021
Coggon, M. M., Gkatzelis, G. I., McDonald, B. C., Gilman, J. B., Schwantes, R. H., Abuhassan, N., Aikin, K. C., Arend, M. F., Berkoff, T. A., Brown, S. S., Campos, T. L., Dickerson, R. R., Gronoff, G., Hurley, J. F., Isaacman-VanWertz, G., Koss, A. R., Li, M., McKeen, S. A., Moshary, F., Peischl, J., Pospisilova, V., Ren, X., Wilson, A., Wu, Y., Trainer, M., and Warneke, C. Volatile chemical product emissions enhance ozone and modulate urban chemistry, Proceedings of the National Academy of Sciences, 118, https://doi.org/10.1073/pnas.2026653118, 2021.
Gkatzelis, G.I.; Identifying Volatile Chemical Product Tracer Compounds in U.S. Cities, Environmental Science & Technology, 55 , 188-199, 2021.
Khare, P. et al.: Ammonium-adduct chemical ionization to investigate anthropogenic oxygenated gas-phase organic compounds in urban air, Atmos. Chem. Phys. Discuss., in review, 2022.
Klein, F. et al.: Characterization of Gas-Phase Organics Using Proton Transfer Reaction Timeof-Flight Mass Spectrometry: Cooking Emissions, Environmental Science & Technology, 50, 1243-1250, 2016
McDonald, B.C. et al.: Volatile chemical products emerging as largest petrochemical source of urban organic emissions, Science, 359, 760-764, 2018
Pye, H. O. T. et al.: Linking gas, particulate, and toxic endpoints to air emissions in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM) version 1.0, Atmos. Chem. Phys. Discuss., in review, 2022.
Xu, L. et al.: A Chemical Ionization Mass Spectrometry Utilizing Ammonium Ions (NH4 + CIMS) for Measurements of Organic Compounds in the Atmosphere, Atmos. Meas. Tech. Discuss., in review, 2022.
Zare, A., Romer, P. S., Nguyen, T., Keutsch, F. N., Skog, K., and Cohen, R. C. A comprehensive organic nitrate chemistry: insights into the lifetime of atmospheric organic nitrates, Atmospheric Chemistry and Physics., 18, 15419–15436, https://doi.org/10.5194/acp-18-15419-2018, 2018.
Journal Articles on this Report : 4 Displayed | Download in RIS Format
Other project views: | All 11 publications | 5 publications in selected types | All 5 journal articles |
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Pfannerstill E, Arata C, Zhu Q, Schulze B, Woods R, Harkins C, Schwantes R, Mcdonald B, Goldstein A. Comparison between Spatially Resolved Airborne Flux Measurements and Emission Inventories of Volatile Organic Compounds in Los Angeles. ENVIRONMENTAL SCIENCE AND TECHNOLOGY 2023;57(41):15533-15545. |
R840010 (2022) R840259 (2023) |
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Place B, Hutzell W, Appel K, Farrell S, Valin L, Murphy B, Seltzer K, Sarwar G, Allen C, Piletic I, D'Ambro E, Saunders E, Simon H, Torres-Vasquez A, Pleim J, Schwantes R, Coggon M, Xu L, Stockwell W, Pye H. Sensitivity of northeastern US surface ozone predictions to the representation of atmospheric chemistry in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMMv1.0). ATMOSPHERIC CHEMISTRY AND PHYSICS 2023;23(16):9173-9190 |
R840010 (2022) |
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Stewart A, Foley M, Doughetry M, Mcgill S, Gulati A, Gentry E, Hagey L, Dorrenstein P, Theirot C, Dodds J, Baker E. Using Multidimensional Separations to Distinguish Isomeric Amino Acid-Bile Acid Conjugates and Assess Their Presence and Perturbations in Model Systems. ANALYTICAL CHEMISTRY 2023;95(41):15357-15366 |
R840010 (2022) |
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Pye HOT, Place BK, Murphy BN, Seltzer KM, D’Ambro EL, Allen C, Piletic IR, Farrell S, Schwantes RH, Coggon MM, Saunders E, Xu L, Sarwar G, Hutzell WT, Foley KM, Pouliot G, et al. Linking gas, particulate, and toxic endpoints to air emissions in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM) version 1.0. Atmospheric Chemistry and Physics Discussions [preprint]. doi:10.5194/acp-2022-695, in review, 2022. |
R840010 (2022) |
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Supplemental Keywords:
Urban ozone, peroxy acyl nitrates, cooking emissions, emission tracers
Relevant Websites:
AEROMMA, SUNVEx/RECAP-CA, FIREX-AQ
Progress and Final Reports:
Original AbstractThe perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.