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Published February 23, 2024 | Version Published
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Nitrate Radicals Suppress Biogenic New Particle Formation from Monoterpene Oxidation

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Abstract

Highly oxygenated organic molecules (HOMs) are a major source of new particles that affect the Earth’s climate. HOM production from the oxidation of volatile organic compounds (VOCs) occurs during both the day and night and can lead to new particle formation (NPF). However, NPF involving organic vapors has been reported much more often during the daytime than during nighttime. Here, we show that the nitrate radicals (NO3), which arise predominantly at night, inhibit NPF during the oxidation of monoterpenes based on three lines of observational evidence: NPF experiments in the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN (European Organization for Nuclear Research), radical chemistry experiments using an oxidation flow reactor, and field observations in a wetland that occasionally exhibits nocturnal NPF. Nitrooxy-peroxy radicals formed from NO3 chemistry suppress the production of ultralow-volatility organic compounds (ULVOCs) responsible for biogenic NPF, which are covalently bound peroxy radical (RO2) dimer association products. The ULVOC yield of α-pinene in the presence of NO3 is one-fifth of that resulting from ozone chemistry alone. Even trace amounts of NO3 radicals, at sub-parts per trillion level, suppress the NPF rate by a factor of 4. Ambient observations further confirm that when NO3 chemistry is involved, monoterpene NPF is completely turned off. Our results explain the frequent absence of nocturnal biogenic NPF in monoterpene (α-pinene)-rich environments.

Copyright and License

© 2024 American Chemical Society.

Acknowledgement

We thank the European Organization for Nuclear Research (CERN) for supporting CLOUD with important technical and financial resources. We thank the Orbitool team for developing the tools to analyze mass spectra and the F0AM people for developing systems to simulate atmospheric chemistry. W.S. thanks the University of Innsbruck for her doctoral scholarship (2021/1). X.C.H. thanks Jenny and Antti Wihuri Foundation for providing funding for this research.

Funding

This work was financially supported by the French National program LEFE (Les Enveloppes Fluides et l’Environnement), the European Research Council (ERC-StG MAARvEL; no. 852161 and ERC-StG CHAPAs; no. 850614), the European Union’s Horizon 2020 Research and Innovation program (Marie Sklodowska-Curie Grant Agreement no. 764991), the Swiss National Science Foundation (200020_172602 and 20FI20_172622), and the US National Science Foundation (AGS-1801574, AGS-1801897, AGS-2132089, and AGS-1801280). The PSI team thanks the European Commission Horizon 2020 Research and Innovation Framework Program, ATMO-ACCESS Integrating Activity (grant agreement no. 101008004). D.D.L. thanks the China Scholarship Council of P. R. China for the Ph.D. grant and support by the State Environment Protection Key Laboratory of Formation and Prevention of Urban Air Pollution Complex (CX2020080582). J.A.T. was supported with a grant from the U.S. Department of Energy Atmospheric System Research Program (DE-SC0021097). H.J. thanks the European Regional Development Fund (project MOBTT42) and Estonian Research Council (project PRG714).

Contributions

D.L. and W.H contributed equally. The manuscript was written through contributions of all authors. D.D.L., D.Y.W., M.Y.W., L.C., B.R., R.M., W.S., H.F., G.M., D.M.B., Z.B., J.C., L.D., J.D., X.D.G., A.H., X.-C.H., V.H., H.J., J.E.K., A.K., H.L., K.L., B.L., N.G.A.M., H.E.M., B.M., S.P., J.P., M.P., M.S., S.S., J.L.S., M.S., S.T., R.V., X.K.W., S.K.W., A.W., D.R.W., Y.S.W., M.Z.-W., M.K., J.K., N.M.D., C.G., I.E.-H., and M.R. prepared the CLOUD facility or measuring instruments. D.D.L., D.Y.W., M.Y.W., L.C., B.R., R.M., W.S., H.F., G.M., D.M.B., J.D., X.D.G., X.-C.H., V.H., H.L., B.L., N.G.A.M., B.M., M.S., J.L.S., M.S., S.K.W., Y.S.W., M.Z.-W., J.K., and M.R. collected the CLOUD data. D.D.L., W.H., D.Y.W., M.Y.W., L.C., B.R., R.M., W.S., H.F., G.M., H.L., S.K.W., and M.R. analyzed the data. D.D.L., D.Y.W., S.P., C.G., I.E.-H., and M.R. planned the flow tube experiments. W.H., H.J., T.P., M.K., and F.B. planned the field campaign and/or data analysis. D.D.L., J.A.T., and M.R. provided model calculations. D.D.L., W.H., D.Y.W., M.Y.W., J.A.T., L.C., B.R., R.M., W.S., H.F., U.B., X.D.G., A.H., H.J., K.L., Y.G.M., B.M., S.P., T.P., S.T., R.V., X.K.W., C.Y., J.K., N.M.D., C.G., I.E.-H., F.B., and M.R. contributed to the scientific discussion. D.D.L., W.H., D.Y.W., M.Y.W., J.A.T., U.B., N.M.D., C.G., I.E.-H., F.B., and M.R. wrote the manuscript. All authors discussed the results and commented on the paper. All authors have given approval to the final version of the manuscript.

Data Availability

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.est.3c07958.

  • Figures S1–S7, S10, S16, and S17 detail the lamps used; sensitivity comparison between mass spectrometers; effect of NO3 radicals and NO on OVOC; evolution of normalized α-pinene reaction rate; simulation of the fate of C10H15O4 and NO3; Kendrick mass defect plots of OVOCs; and the volatility of CHO in the particle phase measured by FIGAERO-CIMS vs estimated by the VBS parametrizations for the CLOUD chamber experiments. Figures S8, S9, and S11–S15 present the gas phase precursors; Kendrick mass defect plots of OVOCs; simulated and observed low oxygenated OVOCs measured by CI-(NH4+)-Orbitrap; distribution of peroxy radicals; and sensitivity of NO3 radicals to the formation of OVOCs for oxidation flow reactor experiments. Figures S18–S21 present nocturnal NPF event and nonevent measured by AIS; Kendrick mass defect plots of oxygenated compounds observed; time evolution of particle number, VOC, O3, and estimated NO3 in a nocturnal NPF event and nonevent; and monoterpene reaction rate in a nocturnal NPF event and nonevent during the Siikaneva campaign.

Conflict of Interest

The authors declare no competing financial interest.

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Additional details

Identifiers

ISSN
1520-5851

Funding

Universität Innsbruck
2021/1
Jenny ja Antti Wihurin Rahasto
European Organization for Nuclear Research
Institut National des Sciences de l'Univers
European Research Council
852161
European Research Council
850614
European Research Council
Marie Skłodowska-Curie Fellowship 764991
Swiss National Science Foundation
200020_172602
Swiss National Science Foundation
20FI20_172622
National Science Foundation
AGS-1801574
National Science Foundation
AGS-1801897
National Science Foundation
AGS-2132089
National Science Foundation
AGS-1801280
European Research Council
101008004
China Scholarship Council
United States Department of Energy
DE-SC0021097
Estonian Research Council
PRG714