Cavity enhanced spectroscopy for measurement of nitrogen oxides in the Anthropocene: Results from the Seoul tower during MAPS 2015

Steven S. Brown, Hyunjin An, Meehye Lee, Jeong Hoo Park, Sang Deok Lee, Dorothy L. Fibiger, Erin E. McDuffie, William P. Dubé, Nicholas L. Wagner, Kyung Eun Min

Research output: Contribution to journalReview article

5 Citations (Scopus)

Abstract

Cavity enhanced spectroscopy, CES, is a high sensitivity direct absorption method that has seen increasing utility in the last decade, a period also marked by increasing requirements for understanding human impacts on atmospheric composition. This paper describes the current NOAA six channel cavity ring-down spectrometer (CRDS, the most common form of CES) for measurement of nitrogen oxides and O3. It further describes the results from measurements from a tower 300 m above the urban area of Seoul in late spring of 2015. The campaign demonstrates the performance of the CRDS instrument and provides new data on both photochemistry and nighttime chemistry in a major Asian megacity. The instrument provided accurate, high time resolution data for N2O5, NO, NO2, NOy and O3, but suffered from large wall loss in the sampling of NO3, illustrating the requirement for calibration of the NO3 inlet transmission. Both the photochemistry and nighttime chemistry of nitrogen oxides and O3 were rapid in this megacity. Sustained average rates of O3 buildup of 10 ppbv h-1 during recurring morning and early afternoon sea breezes led to a 50 ppbv average daily O3 rise. Nitrate radical production rates, P(NO3), averaged 3-4 ppbv h-1 in late afternoon and early evening, much greater than contemporary data from Los Angeles, a comparable U. S. megacity. These P(NO3) were much smaller than historical data from Los Angeles, however. Nighttime data at 300 m above ground showed considerable variability in high time resolution nitrogen oxide and O3, likely resulting from sampling within gradients in the nighttime boundary layer structure. Apparent nighttime biogenic VOC oxidation rates of several ppbv h-1 were also likely influenced by vertical gradients. Finally, daytime N2O5 mixing ratios of 3-35 pptv were associated with rapid daytime P(NO3) and agreed well with a photochemical steady state calculation.

Original languageEnglish
Pages (from-to)529-557
Number of pages29
JournalFaraday Discussions
Volume200
DOIs
Publication statusPublished - 2017

Fingerprint

Nitrogen Oxides
Photochemistry
nitrogen oxides
Los Angeles
Photochemical reactions
towers
Towers
Spectrum Analysis
Atmospheric composition
Spectroscopy
daytime
Sampling
photochemical reactions
cavities
Volatile organic compounds
sampling
Oceans and Seas
Nitrates
chemistry
spectroscopy

ASJC Scopus subject areas

  • Medicine(all)
  • Physical and Theoretical Chemistry

Cite this

Cavity enhanced spectroscopy for measurement of nitrogen oxides in the Anthropocene : Results from the Seoul tower during MAPS 2015. / Brown, Steven S.; An, Hyunjin; Lee, Meehye; Park, Jeong Hoo; Lee, Sang Deok; Fibiger, Dorothy L.; McDuffie, Erin E.; Dubé, William P.; Wagner, Nicholas L.; Min, Kyung Eun.

In: Faraday Discussions, Vol. 200, 2017, p. 529-557.

Research output: Contribution to journalReview article

Brown, SS, An, H, Lee, M, Park, JH, Lee, SD, Fibiger, DL, McDuffie, EE, Dubé, WP, Wagner, NL & Min, KE 2017, 'Cavity enhanced spectroscopy for measurement of nitrogen oxides in the Anthropocene: Results from the Seoul tower during MAPS 2015', Faraday Discussions, vol. 200, pp. 529-557. https://doi.org/10.1039/c7fd00001d
Brown, Steven S. ; An, Hyunjin ; Lee, Meehye ; Park, Jeong Hoo ; Lee, Sang Deok ; Fibiger, Dorothy L. ; McDuffie, Erin E. ; Dubé, William P. ; Wagner, Nicholas L. ; Min, Kyung Eun. / Cavity enhanced spectroscopy for measurement of nitrogen oxides in the Anthropocene : Results from the Seoul tower during MAPS 2015. In: Faraday Discussions. 2017 ; Vol. 200. pp. 529-557.
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abstract = "Cavity enhanced spectroscopy, CES, is a high sensitivity direct absorption method that has seen increasing utility in the last decade, a period also marked by increasing requirements for understanding human impacts on atmospheric composition. This paper describes the current NOAA six channel cavity ring-down spectrometer (CRDS, the most common form of CES) for measurement of nitrogen oxides and O3. It further describes the results from measurements from a tower 300 m above the urban area of Seoul in late spring of 2015. The campaign demonstrates the performance of the CRDS instrument and provides new data on both photochemistry and nighttime chemistry in a major Asian megacity. The instrument provided accurate, high time resolution data for N2O5, NO, NO2, NOy and O3, but suffered from large wall loss in the sampling of NO3, illustrating the requirement for calibration of the NO3 inlet transmission. Both the photochemistry and nighttime chemistry of nitrogen oxides and O3 were rapid in this megacity. Sustained average rates of O3 buildup of 10 ppbv h-1 during recurring morning and early afternoon sea breezes led to a 50 ppbv average daily O3 rise. Nitrate radical production rates, P(NO3), averaged 3-4 ppbv h-1 in late afternoon and early evening, much greater than contemporary data from Los Angeles, a comparable U. S. megacity. These P(NO3) were much smaller than historical data from Los Angeles, however. Nighttime data at 300 m above ground showed considerable variability in high time resolution nitrogen oxide and O3, likely resulting from sampling within gradients in the nighttime boundary layer structure. Apparent nighttime biogenic VOC oxidation rates of several ppbv h-1 were also likely influenced by vertical gradients. Finally, daytime N2O5 mixing ratios of 3-35 pptv were associated with rapid daytime P(NO3) and agreed well with a photochemical steady state calculation.",
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AU - Lee, Sang Deok

AU - Fibiger, Dorothy L.

AU - McDuffie, Erin E.

AU - Dubé, William P.

AU - Wagner, Nicholas L.

AU - Min, Kyung Eun

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