Chemical Differences Between Phenolic Secondary Organic Aerosol Formed Through Gas-Phase and Aqueous-Phase Reactions

Overview

Journal ACS Earth Space Chem

Publisher American Chemical Society

Date 2024 Nov 27

PMID 39600320

Authors

Wenqing Jiang

Lu Yu

Lindsay Yee

Puneet Chhabra

John Seinfeld

Cort Anastasio

Qi Zhang

Affiliations

Soon will be listed here.

Abstract

Phenolic compounds, which are significant emissions from biomass burning (BB), undergo rapid photochemical reactions in both gas and aqueous phases to form secondary organic aerosol, namely, gasSOA and aqSOA, respectively. The formation of gasSOA and aqSOA involves different reaction mechanisms, leading to different product distributions. In this study, we investigate the gaseous and aqueous reactions of guaiacol-a representative BB phenol-to elucidate the compositional differences between phenolic aqSOA and gasSOA. Aqueous-phase reactions of guaiacol produce higher SOA yields than gas-phase reactions (e.g., roughly 60 vs 30% at one half-life of guaiacol). These aqueous reactions involve more complex reaction mechanisms and exhibit a more gradual SOA evolution than their gaseous counterparts. Initially, gasSOA forms with high oxidation levels (O/C > 0.82), while aqSOA starts with lower O/C (0.55-0.75). However, prolonged aqueous-phase reactions substantially increase the oxidation state of aqSOA, making its bulk chemical composition closer to that of gasSOA. Additionally, aqueous reactions form a greater abundance of oligomers and high-molecular-weight compounds, alongside a more sustained production of carboxylic acids. AMS spectral signatures representative of phenolic gasSOA have been identified, which, together with tracer ions of aqSOA, can aid in the interpretation of field observation data on aerosol aging within BB smoke. The notable chemical differences between phenolic gasSOA and aqSOA highlighted in this study also underscore the importance of accurately representing both pathways in atmospheric models to better predict the aerosol properties and their environmental impacts.

References

Vohringer-Martinez E, Hansmann B, Hernandez-Soto H, Hernandez H, Francisco J, Troe J . Water catalysis of a radical-molecule gas-phase reaction. Science. 2007; 315(5811):497-501. DOI: 10.1126/science.1134494. View

Jiang W, Misovich M, Hettiyadura A, Laskin A, McFall A, Anastasio C . Photosensitized Reactions of a Phenolic Carbonyl from Wood Combustion in the Aqueous Phase-Chemical Evolution and Light Absorption Properties of AqSOA. Environ Sci Technol. 2021; 55(8):5199-5211. DOI: 10.1021/acs.est.0c07581. View

McNeill V . Aqueous organic chemistry in the atmosphere: sources and chemical processing of organic aerosols. Environ Sci Technol. 2015; 49(3):1237-44. DOI: 10.1021/es5043707. View

Xu B, Zhang G, Gustafsson O, Kawamura K, Li J, Andersson A . Large contribution of fossil-derived components to aqueous secondary organic aerosols in China. Nat Commun. 2022; 13(1):5115. PMC: 9433442. DOI: 10.1038/s41467-022-32863-3. View

Herrmann H, Schaefer T, Tilgner A, Styler S, Weller C, Teich M . Tropospheric aqueous-phase chemistry: kinetics, mechanisms, and its coupling to a changing gas phase. Chem Rev. 2015; 115(10):4259-334. DOI: 10.1021/cr500447k. View

Ervens B . Modeling the processing of aerosol and trace gases in clouds and fogs. Chem Rev. 2015; 115(10):4157-98. DOI: 10.1021/cr5005887. View

Clark J, English A, Hansen J, Francisco J . Computational study on the existence of organic peroxy radical-water complexes (RO2.H2O). J Phys Chem A. 2008; 112(7):1587-95. DOI: 10.1021/jp077266d. View

Smith J, Sio V, Yu L, Zhang Q, Anastasio C . Secondary organic aerosol production from aqueous reactions of atmospheric phenols with an organic triplet excited state. Environ Sci Technol. 2013; 48(2):1049-57. DOI: 10.1021/es4045715. View

Dong P, Chen Z, Qin X, Gong Y . Water Significantly Changes the Ring-Cleavage Process During Aqueous Photooxidation of Toluene. Environ Sci Technol. 2021; 55(24):16316-16325. DOI: 10.1021/acs.est.1c04770. View

10.

Arciva S, Niedek C, Mavis C, Yoon M, Sanchez M, Zhang Q . Aqueous OH Oxidation of Highly Substituted Phenols as a Source of Secondary Organic Aerosol. Environ Sci Technol. 2022; 56(14):9959-9967. DOI: 10.1021/acs.est.2c02225. View

11.

Simpson C, Naeher L . Biological monitoring of wood-smoke exposure. Inhal Toxicol. 2010; 22(2):99-103. DOI: 10.3109/08958370903008862. View

12.

Bateman A, Nizkorodov S, Laskin J, Laskin A . Photolytic processing of secondary organic aerosols dissolved in cloud droplets. Phys Chem Chem Phys. 2011; 13(26):12199-212. DOI: 10.1039/c1cp20526a. View

13.

Ma L, Guzman C, Niedek C, Tran T, Zhang Q, Anastasio C . Kinetics and Mass Yields of Aqueous Secondary Organic Aerosol from Highly Substituted Phenols Reacting with a Triplet Excited State. Environ Sci Technol. 2021; 55(9):5772-5781. DOI: 10.1021/acs.est.1c00575. View

14.

Faust J, Wong J, Lee A, Abbatt J . Role of Aerosol Liquid Water in Secondary Organic Aerosol Formation from Volatile Organic Compounds. Environ Sci Technol. 2017; 51(3):1405-1413. DOI: 10.1021/acs.est.6b04700. View

15.

Zhang J, Shrivastava M, Ma L, Jiang W, Anastasio C, Zhang Q . Modeling Novel Aqueous Particle and Cloud Chemistry Processes of Biomass Burning Phenols and Their Potential to Form Secondary Organic Aerosols. Environ Sci Technol. 2024; 58(8):3776-3786. DOI: 10.1021/acs.est.3c07762. View

16.

Aiken A, DeCarlo P, Kroll J, Worsnop D, Huffman J, Docherty K . O/C and OM/OC ratios of primary, secondary, and ambient organic aerosols with high-resolution time-of-flight aerosol mass spectrometry. Environ Sci Technol. 2008; 42(12):4478-85. DOI: 10.1021/es703009q. View

17.

El-Sayed M, Hennigan C . Aqueous processing of water-soluble organic compounds in the eastern United States during winter. Environ Sci Process Impacts. 2022; 25(2):241-253. DOI: 10.1039/d2em00115b. View

18.

Wang J, Ye J, Zhang Q, Zhao J, Wu Y, Li J . Aqueous production of secondary organic aerosol from fossil-fuel emissions in winter Beijing haze. Proc Natl Acad Sci U S A. 2021; 118(8). PMC: 7923588. DOI: 10.1073/pnas.2022179118. View

19.

Kaur R, Anastasio C . First Measurements of Organic Triplet Excited States in Atmospheric Waters. Environ Sci Technol. 2018; 52(9):5218-5226. DOI: 10.1021/acs.est.7b06699. View

20.

McFall A, Johnson A, Anastasio C . Air-Water Partitioning of Biomass-Burning Phenols and the Effects of Temperature and Salinity. Environ Sci Technol. 2020; 54(7):3823-3830. DOI: 10.1021/acs.est.9b06443. View