Constraints on Aerosol Nitrate Photolysis as a Potential Source of HONO and NO                         x

Paul S. Romer; Paul J. Wooldridge; John D. Crounse; Michelle J. Kim; Paul O. Wennberg; Jack E. Dibb; Eric Scheuer; Donald R. Blake; Simone Meinardi; Alexandra L. Brosius; Alexander B. Thames; David O. Miller; William H. Brune; Samuel R. Hall; Thomas B. Ryerson; Ronald C. Cohen

doi:10.1021/acs.est.8b03861

Constraints on Aerosol Nitrate Photolysis as a Potential Source of HONO and NO _x

Paul S. Romer, Paul J. Wooldridge, John D. Crounse, Michelle J. Kim, Paul O. Wennberg, Jack E. Dibb, Eric Scheuer, Donald R. Blake, Simone Meinardi, Alexandra L. Brosius, Alexander B. Thames, David O. Miller, William H. Brune, Samuel R. Hall, Thomas B. Ryerson, Ronald C. Cohen

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

17 Scopus citations

Abstract

The concentration of nitrogen oxides (NO _x ) plays a central role in controlling air quality. On a global scale, the primary sink of NO _x is oxidation to form HNO ₃ . Gas-phase HNO ₃ photolyses slowly with a lifetime in the troposphere of 10 days or more. However, several recent studies examining HONO chemistry have proposed that particle-phase HNO ₃ undergoes photolysis 10-300 times more rapidly than gas-phase HNO ₃ . We present here constraints on the rate of particle-phase HNO ₃ photolysis based on observations of NO _x and HNO ₃ collected over the Yellow Sea during the KORUS-AQ study in summer 2016. The fastest proposed photolysis rates are inconsistent with the observed NO _x to HNO ₃ ratios. Negligible to moderate enhancements of the HNO ₃ photolysis rate in particles, 1-30 times faster than in the gas phase, are most consistent with the observations. Small or moderate enhancement of particle-phase HNO ₃ photolysis would not significantly affect the HNO ₃ budget but could help explain observations of HONO and NO _x in highly aged air.

Original language	English (US)
Pages (from-to)	13738-13746
Number of pages	9
Journal	Environmental Science and Technology
Volume	52
Issue number	23
DOIs	https://doi.org/10.1021/acs.est.8b03861
State	Published - Dec 4 2018

All Science Journal Classification (ASJC) codes

Chemistry(all)
Environmental Chemistry

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Romer, P. S., Wooldridge, P. J., Crounse, J. D., Kim, M. J., Wennberg, P. O., Dibb, J. E., Scheuer, E., Blake, D. R., Meinardi, S., Brosius, A. L., Thames, A. B., Miller, D. O., Brune, W. H., Hall, S. R., Ryerson, T. B., & Cohen, R. C. (2018). Constraints on Aerosol Nitrate Photolysis as a Potential Source of HONO and NO _x Environmental Science and Technology, 52(23), 13738-13746. https://doi.org/10.1021/acs.est.8b03861

Romer, Paul S. ; Wooldridge, Paul J. ; Crounse, John D. ; Kim, Michelle J. ; Wennberg, Paul O. ; Dibb, Jack E. ; Scheuer, Eric ; Blake, Donald R. ; Meinardi, Simone ; Brosius, Alexandra L. ; Thames, Alexander B. ; Miller, David O. ; Brune, William H. ; Hall, Samuel R. ; Ryerson, Thomas B. ; Cohen, Ronald C. / Constraints on Aerosol Nitrate Photolysis as a Potential Source of HONO and NO _x In: Environmental Science and Technology. 2018 ; Vol. 52, No. 23. pp. 13738-13746.

@article{76c032a350424ed788d60e3618fd8ffa,

title = " Constraints on Aerosol Nitrate Photolysis as a Potential Source of HONO and NO x ",

abstract = " The concentration of nitrogen oxides (NO x ) plays a central role in controlling air quality. On a global scale, the primary sink of NO x is oxidation to form HNO 3 . Gas-phase HNO 3 photolyses slowly with a lifetime in the troposphere of 10 days or more. However, several recent studies examining HONO chemistry have proposed that particle-phase HNO 3 undergoes photolysis 10-300 times more rapidly than gas-phase HNO 3 . We present here constraints on the rate of particle-phase HNO 3 photolysis based on observations of NO x and HNO 3 collected over the Yellow Sea during the KORUS-AQ study in summer 2016. The fastest proposed photolysis rates are inconsistent with the observed NO x to HNO 3 ratios. Negligible to moderate enhancements of the HNO 3 photolysis rate in particles, 1-30 times faster than in the gas phase, are most consistent with the observations. Small or moderate enhancement of particle-phase HNO 3 photolysis would not significantly affect the HNO 3 budget but could help explain observations of HONO and NO x in highly aged air. ",

author = "Romer, {Paul S.} and Wooldridge, {Paul J.} and Crounse, {John D.} and Kim, {Michelle J.} and Wennberg, {Paul O.} and Dibb, {Jack E.} and Eric Scheuer and Blake, {Donald R.} and Simone Meinardi and Brosius, {Alexandra L.} and Thames, {Alexander B.} and Miller, {David O.} and Brune, {William H.} and Hall, {Samuel R.} and Ryerson, {Thomas B.} and Cohen, {Ronald C.}",

note = "Funding Information: We thank NASA for support via NNX15AT85G (Berkeley), NNX15AT97G and NNX14AP46G (Caltech), NNX14AP46G (UNH), and NNX16AD96G (to C.K.). M.J.K. was supported by NSF AGS Award No. 1524860. Methanol and acetaldehyde measurements were supported by the Austrian Federal Ministry for Transport, Innovation and Technology (bmvit) through the Austrian Research Promotion Agency (FFG). The authors thank Alan Fried for the formaldehyde measurements, Armin Wisthaler for the methanol and acetaldehyde measurements, Christoph Knote for the FLEXPART model results, Glenn Diskin for the CH4 and CO measurements, and Andrew Weinheimer and Denise Montzka for NO measurements. We thank Tamara Sparks and Alex Teng for assistance in the field, the ground and flight crew of the DC-8, and the KORUS-AQ science team.",

year = "2018",

month = dec,

day = "4",

doi = "10.1021/acs.est.8b03861",

language = "English (US)",

volume = "52",

pages = "13738--13746",

journal = "Environmental Science & Technology",

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publisher = "American Chemical Society",

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Romer, PS, Wooldridge, PJ, Crounse, JD, Kim, MJ, Wennberg, PO, Dibb, JE, Scheuer, E, Blake, DR, Meinardi, S, Brosius, AL, Thames, AB , Miller, DO , Brune, WH, Hall, SR, Ryerson, TB & Cohen, RC 2018, ' Constraints on Aerosol Nitrate Photolysis as a Potential Source of HONO and NO _x ', Environmental Science and Technology, vol. 52, no. 23, pp. 13738-13746. https://doi.org/10.1021/acs.est.8b03861

Constraints on Aerosol Nitrate Photolysis as a Potential Source of HONO and NO _x . / Romer, Paul S.; Wooldridge, Paul J.; Crounse, John D.; Kim, Michelle J.; Wennberg, Paul O.; Dibb, Jack E.; Scheuer, Eric; Blake, Donald R.; Meinardi, Simone; Brosius, Alexandra L.; Thames, Alexander B.; Miller, David O.; Brune, William H.; Hall, Samuel R.; Ryerson, Thomas B.; Cohen, Ronald C.

In: Environmental Science and Technology, Vol. 52, No. 23, 04.12.2018, p. 13738-13746.

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

TY - JOUR

T1 - Constraints on Aerosol Nitrate Photolysis as a Potential Source of HONO and NO x

AU - Romer, Paul S.

AU - Wooldridge, Paul J.

AU - Crounse, John D.

AU - Kim, Michelle J.

AU - Wennberg, Paul O.

AU - Dibb, Jack E.

AU - Scheuer, Eric

AU - Blake, Donald R.

AU - Meinardi, Simone

AU - Brosius, Alexandra L.

AU - Thames, Alexander B.

AU - Miller, David O.

AU - Brune, William H.

AU - Hall, Samuel R.

AU - Ryerson, Thomas B.

AU - Cohen, Ronald C.

N1 - Funding Information: We thank NASA for support via NNX15AT85G (Berkeley), NNX15AT97G and NNX14AP46G (Caltech), NNX14AP46G (UNH), and NNX16AD96G (to C.K.). M.J.K. was supported by NSF AGS Award No. 1524860. Methanol and acetaldehyde measurements were supported by the Austrian Federal Ministry for Transport, Innovation and Technology (bmvit) through the Austrian Research Promotion Agency (FFG). The authors thank Alan Fried for the formaldehyde measurements, Armin Wisthaler for the methanol and acetaldehyde measurements, Christoph Knote for the FLEXPART model results, Glenn Diskin for the CH4 and CO measurements, and Andrew Weinheimer and Denise Montzka for NO measurements. We thank Tamara Sparks and Alex Teng for assistance in the field, the ground and flight crew of the DC-8, and the KORUS-AQ science team.

PY - 2018/12/4

Y1 - 2018/12/4

N2 - The concentration of nitrogen oxides (NO x ) plays a central role in controlling air quality. On a global scale, the primary sink of NO x is oxidation to form HNO 3 . Gas-phase HNO 3 photolyses slowly with a lifetime in the troposphere of 10 days or more. However, several recent studies examining HONO chemistry have proposed that particle-phase HNO 3 undergoes photolysis 10-300 times more rapidly than gas-phase HNO 3 . We present here constraints on the rate of particle-phase HNO 3 photolysis based on observations of NO x and HNO 3 collected over the Yellow Sea during the KORUS-AQ study in summer 2016. The fastest proposed photolysis rates are inconsistent with the observed NO x to HNO 3 ratios. Negligible to moderate enhancements of the HNO 3 photolysis rate in particles, 1-30 times faster than in the gas phase, are most consistent with the observations. Small or moderate enhancement of particle-phase HNO 3 photolysis would not significantly affect the HNO 3 budget but could help explain observations of HONO and NO x in highly aged air.

AB - The concentration of nitrogen oxides (NO x ) plays a central role in controlling air quality. On a global scale, the primary sink of NO x is oxidation to form HNO 3 . Gas-phase HNO 3 photolyses slowly with a lifetime in the troposphere of 10 days or more. However, several recent studies examining HONO chemistry have proposed that particle-phase HNO 3 undergoes photolysis 10-300 times more rapidly than gas-phase HNO 3 . We present here constraints on the rate of particle-phase HNO 3 photolysis based on observations of NO x and HNO 3 collected over the Yellow Sea during the KORUS-AQ study in summer 2016. The fastest proposed photolysis rates are inconsistent with the observed NO x to HNO 3 ratios. Negligible to moderate enhancements of the HNO 3 photolysis rate in particles, 1-30 times faster than in the gas phase, are most consistent with the observations. Small or moderate enhancement of particle-phase HNO 3 photolysis would not significantly affect the HNO 3 budget but could help explain observations of HONO and NO x in highly aged air.

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U2 - 10.1021/acs.est.8b03861

DO - 10.1021/acs.est.8b03861

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VL - 52

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EP - 13746

JO - Environmental Science & Technology

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SN - 0013-936X

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