Key role of NO3 radicals in the production of isoprene nitrates and nitrooxyorganosulfates in Beijing

Jacqueline F. Hamilton; Daniel J. Bryant; Peter M. Edwards; Bin Ouyang; Thomas J. Bannan; Archit Mehra; Alfred W. Mayhew; James R. Hopkins; Rachel E. Dunmore; Freya A. Squires; James D. Lee; Mike J. Newland; Stephen D. Worrall; Asan Bacak; Hugh Coe; Carl J.  Percival; Lisa K. Whalley; Dwayne E. Heard; Eloise J. Slater; Roderic L. Jones; Tianqu Cui; Jason D. Surratt; Claire E. Reeves; Graham P. Mills; Sue Grimmond; Yele Sun; Weiqi Xu; Zongbo Shi; Andrew R. Rickard

doi:10.1021/acs.est.0c05689

Key role of NO₃ radicals in the production of isoprene nitrates and nitrooxyorganosulfates in Beijing

Jacqueline F. Hamilton^*, Daniel J. Bryant, Peter M. Edwards, Bin Ouyang, Thomas J. Bannan, Archit Mehra, Alfred W. Mayhew, James R. Hopkins, Rachel E. Dunmore, Freya A. Squires, James D. Lee, Mike J. Newland, Stephen D. Worrall, Asan Bacak, Hugh Coe, Carl J. Percival, Lisa K. Whalley, Dwayne E. Heard, Eloise J. Slater, Roderic L. JonesTianqu Cui, Jason D. Surratt, Claire E. Reeves, Graham P. Mills, Sue Grimmond, Yele Sun, Weiqi Xu, Zongbo Shi, Andrew R. Rickard

^*Corresponding author for this work

Earth and Environmental Sciences

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

The formation of isoprene nitrates (IsN) can lead to significant secondary organic aerosol (SOA) production and they can act as reservoirs of atmospheric nitrogen oxides. In this work, we estimate the rate of production of IsN from the reactions of isoprene with OH and NO3 radicals during the summertime in Beijing. While OH dominates the loss of isoprene during the day, NO3 plays an increasingly important role in the production of IsN from the early afternoon onwards. Unusually low NO concentrations during the afternoon resulted in NO3 mixing ratios of ca. 2 pptv at approximately 15:00, which we estimate to account for around a third of the total IsN production in the gas phase. Heterogeneous uptake of IsN produces nitrooxyorganosulfates (NOS). Two mono-nitrated NOS were correlated with particulate sulfate concentrations and appear to be formed from sequential NO3 and OH oxidation. Di- and tri-nitrated isoprene-related NOS, formed from multiple NO3 oxidation steps, peaked during the night. This work highlights that NO3 chemistry can play a key role in driving biogenic-anthropogenic interactive chemistry in Beijing with respect to the formation of IsN during both the day and night.

Original language	English
Pages (from-to)	842-853
Number of pages	12
Journal	Environmental Science and Technology
Volume	55
Issue number	2
Early online date	7 Jan 2021
DOIs	https://doi.org/10.1021/acs.est.0c05689
Publication status	Published - 19 Jan 2021

Bibliographical note

Funding Information:
This project was funded by the Natural Environment Research Council, the Newton Fund and Medical Research Council in the U.K., and the National Natural Science Foundation of China (NE/N00700X/1, NE/N00695X/1, NE/N006895/1, NE/N007190/1, NE/N006917/1, NE/N006909/1). D.J.B., F.A.S., and E.J.S. acknowledge NERC SPHERES Ph.D. studentships. A.W.M. acknowledges a NERC PANORAMA Ph.D. studentship. P.M.E acknowledges funding the European Research Council Grant ERC-StG-802685. The Orbitrap-MS was funded by a Natural Environment Research Council strategic capital grant, CC090. J.D.S. and T.C. acknowledge support from the United States National Science Foundation (NSF) under Atmospheric and Geospace (AGS) Grant 1703535.

ASJC Scopus subject areas

Chemistry(all)
Environmental Chemistry

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Cite this

Hamilton, J. F., Bryant, D. J., Edwards, P. M., Ouyang, B., Bannan, T. J., Mehra, A., Mayhew, A. W., Hopkins, J. R., Dunmore, R. E., Squires, F. A., Lee, J. D., Newland, M. J., Worrall, S. D., Bacak, A., Coe, H., Percival, C. J., Whalley, L. K., Heard, D. E., Slater, E. J., ... Rickard, A. R. (2021). Key role of NO₃ radicals in the production of isoprene nitrates and nitrooxyorganosulfates in Beijing. Environmental Science and Technology, 55(2), 842-853. Advance online publication. https://doi.org/10.1021/acs.est.0c05689

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title = "Key role of NO3 radicals in the production of isoprene nitrates and nitrooxyorganosulfates in Beijing",

abstract = "The formation of isoprene nitrates (IsN) can lead to significant secondary organic aerosol (SOA) production and they can act as reservoirs of atmospheric nitrogen oxides. In this work, we estimate the rate of production of IsN from the reactions of isoprene with OH and NO3 radicals during the summertime in Beijing. While OH dominates the loss of isoprene during the day, NO3 plays an increasingly important role in the production of IsN from the early afternoon onwards. Unusually low NO concentrations during the afternoon resulted in NO3 mixing ratios of ca. 2 pptv at approximately 15:00, which we estimate to account for around a third of the total IsN production in the gas phase. Heterogeneous uptake of IsN produces nitrooxyorganosulfates (NOS). Two mono-nitrated NOS were correlated with particulate sulfate concentrations and appear to be formed from sequential NO3 and OH oxidation. Di- and tri-nitrated isoprene-related NOS, formed from multiple NO3 oxidation steps, peaked during the night. This work highlights that NO3 chemistry can play a key role in driving biogenic-anthropogenic interactive chemistry in Beijing with respect to the formation of IsN during both the day and night.",

author = "Hamilton, {Jacqueline F.} and Bryant, {Daniel J.} and Edwards, {Peter M.} and Bin Ouyang and Bannan, {Thomas J.} and Archit Mehra and Mayhew, {Alfred W.} and Hopkins, {James R.} and Dunmore, {Rachel E.} and Squires, {Freya A.} and Lee, {James D.} and Newland, {Mike J.} and Worrall, {Stephen D.} and Asan Bacak and Hugh Coe and Percival, {Carl J.} and Whalley, {Lisa K.} and Heard, {Dwayne E.} and Slater, {Eloise J.} and Jones, {Roderic L.} and Tianqu Cui and Surratt, {Jason D.} and Reeves, {Claire E.} and Mills, {Graham P.} and Sue Grimmond and Yele Sun and Weiqi Xu and Zongbo Shi and Rickard, {Andrew R.}",

note = "Funding Information: This project was funded by the Natural Environment Research Council, the Newton Fund and Medical Research Council in the U.K., and the National Natural Science Foundation of China (NE/N00700X/1, NE/N00695X/1, NE/N006895/1, NE/N007190/1, NE/N006917/1, NE/N006909/1). D.J.B., F.A.S., and E.J.S. acknowledge NERC SPHERES Ph.D. studentships. A.W.M. acknowledges a NERC PANORAMA Ph.D. studentship. P.M.E acknowledges funding the European Research Council Grant ERC-StG-802685. The Orbitrap-MS was funded by a Natural Environment Research Council strategic capital grant, CC090. J.D.S. and T.C. acknowledge support from the United States National Science Foundation (NSF) under Atmospheric and Geospace (AGS) Grant 1703535. ",

year = "2021",

month = jan,

day = "19",

doi = "10.1021/acs.est.0c05689",

language = "English",

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journal = "Environmental Science and Technology",

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Hamilton, JF, Bryant, DJ, Edwards, PM, Ouyang, B, Bannan, TJ, Mehra, A, Mayhew, AW, Hopkins, JR, Dunmore, RE, Squires, FA, Lee, JD, Newland, MJ, Worrall, SD, Bacak, A, Coe, H, Percival, CJ, Whalley, LK, Heard, DE, Slater, EJ, Jones, RL, Cui, T, Surratt, JD, Reeves, CE, Mills, GP, Grimmond, S, Sun, Y, Xu, W, Shi, Z & Rickard, AR 2021, 'Key role of NO₃ radicals in the production of isoprene nitrates and nitrooxyorganosulfates in Beijing', Environmental Science and Technology, vol. 55, no. 2, pp. 842-853. https://doi.org/10.1021/acs.est.0c05689

TY - JOUR

T1 - Key role of NO3 radicals in the production of isoprene nitrates and nitrooxyorganosulfates in Beijing

AU - Hamilton, Jacqueline F.

AU - Bryant, Daniel J.

AU - Edwards, Peter M.

AU - Ouyang, Bin

AU - Bannan, Thomas J.

AU - Mehra, Archit

AU - Mayhew, Alfred W.

AU - Hopkins, James R.

AU - Dunmore, Rachel E.

AU - Squires, Freya A.

AU - Lee, James D.

AU - Newland, Mike J.

AU - Worrall, Stephen D.

AU - Bacak, Asan

AU - Coe, Hugh

AU - Percival, Carl J.

AU - Whalley, Lisa K.

AU - Heard, Dwayne E.

AU - Slater, Eloise J.

AU - Jones, Roderic L.

AU - Cui, Tianqu

AU - Surratt, Jason D.

AU - Reeves, Claire E.

AU - Mills, Graham P.

AU - Grimmond, Sue

AU - Sun, Yele

AU - Xu, Weiqi

AU - Shi, Zongbo

AU - Rickard, Andrew R.

N1 - Funding Information: This project was funded by the Natural Environment Research Council, the Newton Fund and Medical Research Council in the U.K., and the National Natural Science Foundation of China (NE/N00700X/1, NE/N00695X/1, NE/N006895/1, NE/N007190/1, NE/N006917/1, NE/N006909/1). D.J.B., F.A.S., and E.J.S. acknowledge NERC SPHERES Ph.D. studentships. A.W.M. acknowledges a NERC PANORAMA Ph.D. studentship. P.M.E acknowledges funding the European Research Council Grant ERC-StG-802685. The Orbitrap-MS was funded by a Natural Environment Research Council strategic capital grant, CC090. J.D.S. and T.C. acknowledge support from the United States National Science Foundation (NSF) under Atmospheric and Geospace (AGS) Grant 1703535.

PY - 2021/1/19

Y1 - 2021/1/19

N2 - The formation of isoprene nitrates (IsN) can lead to significant secondary organic aerosol (SOA) production and they can act as reservoirs of atmospheric nitrogen oxides. In this work, we estimate the rate of production of IsN from the reactions of isoprene with OH and NO3 radicals during the summertime in Beijing. While OH dominates the loss of isoprene during the day, NO3 plays an increasingly important role in the production of IsN from the early afternoon onwards. Unusually low NO concentrations during the afternoon resulted in NO3 mixing ratios of ca. 2 pptv at approximately 15:00, which we estimate to account for around a third of the total IsN production in the gas phase. Heterogeneous uptake of IsN produces nitrooxyorganosulfates (NOS). Two mono-nitrated NOS were correlated with particulate sulfate concentrations and appear to be formed from sequential NO3 and OH oxidation. Di- and tri-nitrated isoprene-related NOS, formed from multiple NO3 oxidation steps, peaked during the night. This work highlights that NO3 chemistry can play a key role in driving biogenic-anthropogenic interactive chemistry in Beijing with respect to the formation of IsN during both the day and night.

AB - The formation of isoprene nitrates (IsN) can lead to significant secondary organic aerosol (SOA) production and they can act as reservoirs of atmospheric nitrogen oxides. In this work, we estimate the rate of production of IsN from the reactions of isoprene with OH and NO3 radicals during the summertime in Beijing. While OH dominates the loss of isoprene during the day, NO3 plays an increasingly important role in the production of IsN from the early afternoon onwards. Unusually low NO concentrations during the afternoon resulted in NO3 mixing ratios of ca. 2 pptv at approximately 15:00, which we estimate to account for around a third of the total IsN production in the gas phase. Heterogeneous uptake of IsN produces nitrooxyorganosulfates (NOS). Two mono-nitrated NOS were correlated with particulate sulfate concentrations and appear to be formed from sequential NO3 and OH oxidation. Di- and tri-nitrated isoprene-related NOS, formed from multiple NO3 oxidation steps, peaked during the night. This work highlights that NO3 chemistry can play a key role in driving biogenic-anthropogenic interactive chemistry in Beijing with respect to the formation of IsN during both the day and night.

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U2 - 10.1021/acs.est.0c05689

DO - 10.1021/acs.est.0c05689

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