Hydrogen peroxide and methylhydroperoxide distributions related to ozone and odd hydrogen over the North Pacific in the fall of 1991

Brian G. Heikes, Meehye Lee, J. Bradshaw, S. Sandholm, D. D. Davis, J. Crawford, Jose Rodriguez, S. Liu, S. McKeen, D. Thornton, A. Bandy, G. Gregory, R. Talbot, D. Blake

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

Hydrogen peroxide and methylhydroperoxide were measured in the troposphere over the western North Pacific as part of the airborne portion of NASA's Global Tropospheric Experiment/Pacific Exploratory Mission-West A field mission. The flights circled the North Pacific, focusing on the western Pacific, and extended from 300 to 13,000 m altitude. The hydroperoxides were uniquely separated and quantified using a high-pressure liquid chromatography system in conjunction with a continuous enzyme fluorometric instrument. Results show a latitudinal gradient in both peroxides at all altitudes; for example, between 3 and 5 km, H2O2 median values decrease from 1700 to 500 parts per trillion by volume (pptv) in going from 0°-15°N to 45°-60°N, and the corresponding decrease in CH3OOH was 1100 to 200 pptv. Concentration maxima are observed in both species at altitudes of 2 to 3 km with H2O2 concentrations below 1 km lower by 30%, 10% for CH3OOH, and even lower, by a factor of 10, for both above 9 km. The H2O2 to CH3OOH ratio increased with altitude and latitude with ratios <1 in the tropical surface layer and >2 at midlatitude high altitude. Highest peroxide concentrations were encountered over the Celebes Sea in air which was impacted by aged biomass fire and urban pollutants. CH3OOH was below the level of detection in stratospheric air. H2O2 exceeded SO2 95% of the time, with the exceptions generally above 9 km. Above 3 km, O3 increases with decreasing H2O2 and CH3OOH. Below 3 km the O3-CH3OOH trend is the same but O3 increases with increasing H2O2. The measurements are compared with predictions based upon a photochemical steady state zero-dimensional model and a three-dimensional mesoscale time-dependent model. These models capture observed trends in H2O2 and CH3OOH, with the possible exception of H2O2 below 2 km where surface removal is important. A surface removal lifetime of 3.5 days brings the observed and zero-dimensional model-estimated H2O2 into agreement. The steady state model suggests a strong correlation between the ratios of NO/CO or HO2/HO and the ratio of H2O2/CH3OOH. The observed hydroperoxide ratios bracket the modeled relationship with occasionally much lower H2O2 than expected.

Original languageEnglish
Pages (from-to)1891-1905
Number of pages15
JournalJournal of Geophysical Research D: Atmospheres
Volume101
Issue numberD1
Publication statusPublished - 1996 Dec 1
Externally publishedYes

Fingerprint

Ozone
hydrogen peroxide
Hydrogen Peroxide
ozone
Hydrogen
hydrogen
Peroxides
peroxides
High pressure liquid chromatography
trends
Upper atmosphere
Troposphere
temperate regions
latitudinal gradient
air
liquid chromatography
Carbon Monoxide
high altitude
brackets
biomass

ASJC Scopus subject areas

  • Oceanography
  • Astronomy and Astrophysics
  • Atmospheric Science
  • Space and Planetary Science
  • Earth and Planetary Sciences (miscellaneous)
  • Geophysics
  • Geochemistry and Petrology
  • Earth and Planetary Sciences(all)
  • Environmental Science(all)

Cite this

Hydrogen peroxide and methylhydroperoxide distributions related to ozone and odd hydrogen over the North Pacific in the fall of 1991. / Heikes, Brian G.; Lee, Meehye; Bradshaw, J.; Sandholm, S.; Davis, D. D.; Crawford, J.; Rodriguez, Jose; Liu, S.; McKeen, S.; Thornton, D.; Bandy, A.; Gregory, G.; Talbot, R.; Blake, D.

In: Journal of Geophysical Research D: Atmospheres, Vol. 101, No. D1, 01.12.1996, p. 1891-1905.

Research output: Contribution to journalArticle

Heikes, BG, Lee, M, Bradshaw, J, Sandholm, S, Davis, DD, Crawford, J, Rodriguez, J, Liu, S, McKeen, S, Thornton, D, Bandy, A, Gregory, G, Talbot, R & Blake, D 1996, 'Hydrogen peroxide and methylhydroperoxide distributions related to ozone and odd hydrogen over the North Pacific in the fall of 1991', Journal of Geophysical Research D: Atmospheres, vol. 101, no. D1, pp. 1891-1905.
Heikes, Brian G. ; Lee, Meehye ; Bradshaw, J. ; Sandholm, S. ; Davis, D. D. ; Crawford, J. ; Rodriguez, Jose ; Liu, S. ; McKeen, S. ; Thornton, D. ; Bandy, A. ; Gregory, G. ; Talbot, R. ; Blake, D. / Hydrogen peroxide and methylhydroperoxide distributions related to ozone and odd hydrogen over the North Pacific in the fall of 1991. In: Journal of Geophysical Research D: Atmospheres. 1996 ; Vol. 101, No. D1. pp. 1891-1905.
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abstract = "Hydrogen peroxide and methylhydroperoxide were measured in the troposphere over the western North Pacific as part of the airborne portion of NASA's Global Tropospheric Experiment/Pacific Exploratory Mission-West A field mission. The flights circled the North Pacific, focusing on the western Pacific, and extended from 300 to 13,000 m altitude. The hydroperoxides were uniquely separated and quantified using a high-pressure liquid chromatography system in conjunction with a continuous enzyme fluorometric instrument. Results show a latitudinal gradient in both peroxides at all altitudes; for example, between 3 and 5 km, H2O2 median values decrease from 1700 to 500 parts per trillion by volume (pptv) in going from 0°-15°N to 45°-60°N, and the corresponding decrease in CH3OOH was 1100 to 200 pptv. Concentration maxima are observed in both species at altitudes of 2 to 3 km with H2O2 concentrations below 1 km lower by 30{\%}, 10{\%} for CH3OOH, and even lower, by a factor of 10, for both above 9 km. The H2O2 to CH3OOH ratio increased with altitude and latitude with ratios <1 in the tropical surface layer and >2 at midlatitude high altitude. Highest peroxide concentrations were encountered over the Celebes Sea in air which was impacted by aged biomass fire and urban pollutants. CH3OOH was below the level of detection in stratospheric air. H2O2 exceeded SO2 95{\%} of the time, with the exceptions generally above 9 km. Above 3 km, O3 increases with decreasing H2O2 and CH3OOH. Below 3 km the O3-CH3OOH trend is the same but O3 increases with increasing H2O2. The measurements are compared with predictions based upon a photochemical steady state zero-dimensional model and a three-dimensional mesoscale time-dependent model. These models capture observed trends in H2O2 and CH3OOH, with the possible exception of H2O2 below 2 km where surface removal is important. A surface removal lifetime of 3.5 days brings the observed and zero-dimensional model-estimated H2O2 into agreement. The steady state model suggests a strong correlation between the ratios of NO/CO or HO2/HO and the ratio of H2O2/CH3OOH. The observed hydroperoxide ratios bracket the modeled relationship with occasionally much lower H2O2 than expected.",
author = "Heikes, {Brian G.} and Meehye Lee and J. Bradshaw and S. Sandholm and Davis, {D. D.} and J. Crawford and Jose Rodriguez and S. Liu and S. McKeen and D. Thornton and A. Bandy and G. Gregory and R. Talbot and D. Blake",
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T1 - Hydrogen peroxide and methylhydroperoxide distributions related to ozone and odd hydrogen over the North Pacific in the fall of 1991

AU - Heikes, Brian G.

AU - Lee, Meehye

AU - Bradshaw, J.

AU - Sandholm, S.

AU - Davis, D. D.

AU - Crawford, J.

AU - Rodriguez, Jose

AU - Liu, S.

AU - McKeen, S.

AU - Thornton, D.

AU - Bandy, A.

AU - Gregory, G.

AU - Talbot, R.

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N2 - Hydrogen peroxide and methylhydroperoxide were measured in the troposphere over the western North Pacific as part of the airborne portion of NASA's Global Tropospheric Experiment/Pacific Exploratory Mission-West A field mission. The flights circled the North Pacific, focusing on the western Pacific, and extended from 300 to 13,000 m altitude. The hydroperoxides were uniquely separated and quantified using a high-pressure liquid chromatography system in conjunction with a continuous enzyme fluorometric instrument. Results show a latitudinal gradient in both peroxides at all altitudes; for example, between 3 and 5 km, H2O2 median values decrease from 1700 to 500 parts per trillion by volume (pptv) in going from 0°-15°N to 45°-60°N, and the corresponding decrease in CH3OOH was 1100 to 200 pptv. Concentration maxima are observed in both species at altitudes of 2 to 3 km with H2O2 concentrations below 1 km lower by 30%, 10% for CH3OOH, and even lower, by a factor of 10, for both above 9 km. The H2O2 to CH3OOH ratio increased with altitude and latitude with ratios <1 in the tropical surface layer and >2 at midlatitude high altitude. Highest peroxide concentrations were encountered over the Celebes Sea in air which was impacted by aged biomass fire and urban pollutants. CH3OOH was below the level of detection in stratospheric air. H2O2 exceeded SO2 95% of the time, with the exceptions generally above 9 km. Above 3 km, O3 increases with decreasing H2O2 and CH3OOH. Below 3 km the O3-CH3OOH trend is the same but O3 increases with increasing H2O2. The measurements are compared with predictions based upon a photochemical steady state zero-dimensional model and a three-dimensional mesoscale time-dependent model. These models capture observed trends in H2O2 and CH3OOH, with the possible exception of H2O2 below 2 km where surface removal is important. A surface removal lifetime of 3.5 days brings the observed and zero-dimensional model-estimated H2O2 into agreement. The steady state model suggests a strong correlation between the ratios of NO/CO or HO2/HO and the ratio of H2O2/CH3OOH. The observed hydroperoxide ratios bracket the modeled relationship with occasionally much lower H2O2 than expected.

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