In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

B. B. Palm, P. Campuzano-Jost, A. M. Ortega, D. A. Day, L. Kaser, W. Jud, T. Karl, A. Hansel, J. F. Hunter, E. S. Cross, J. H. Kroll, Z. Peng, William Henry Brune, J. L. Jimenez

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Ambient air was oxidized by OH radicals in an oxidation flow reactor (OFR) located in a montane pine forest during the BEACHON-RoMBAS campaign to study biogenic secondary organic aerosol (SOA) formation and aging. High OH concentrations and short residence times allowed for semi-continuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative time scales of condensation of low volatility organic compounds (LVOCs) onto particles, condensational loss to the walls, and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 4 μg m-3 when LVOC fate corrected) compared to daytime (average 1 μg m-3 when LVOC fate corrected), with maximum formation observed at 0.4-1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene + p-cymene concentrations, including a substantial increase just after sunrise at 07:00 LT. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 6 times more SOA was formed in the reactor from OH oxidation than could be explained by the VOCs measured in ambient air. Several recently-developed instruments quantified ambient semi- and intermediate-volatility organic compounds (S/IVOCs) that were not detected by a PTR-TOF-MS. An SOA yield of 24-80 % from those compounds can explain the observed SOA, suggesting that these typically unmeasured S/IVOCs play a substantial role in ambient SOA formation. Our results allow ruling out condensation sticking coefficients much lower than 1. Our measurements help clarify the magnitude of SOA formation in forested environments, and demonstrate methods for interpretation of ambient OFR measurements.

Original languageEnglish (US)
Pages (from-to)30409-30471
Number of pages63
JournalAtmospheric Chemistry and Physics Discussions
Volume15
Issue number21
DOIs
StatePublished - Nov 4 2015

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aerosol formation
aerosols
reactors
oxidation
organic compound
air
organic compounds
volatility
aerosol
ambient air
volatile organic compound
condensation
volatile organic compounds
fragmentation
reactor
in situ
monoterpene
montane forest
volatilization
gas

All Science Journal Classification (ASJC) codes

  • Atmospheric Science
  • Space and Planetary Science

Cite this

Palm, B. B., Campuzano-Jost, P., Ortega, A. M., Day, D. A., Kaser, L., Jud, W., ... Jimenez, J. L. (2015). In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor. Atmospheric Chemistry and Physics Discussions, 15(21), 30409-30471. https://doi.org/10.5194/acpd-15-30409-2015
Palm, B. B. ; Campuzano-Jost, P. ; Ortega, A. M. ; Day, D. A. ; Kaser, L. ; Jud, W. ; Karl, T. ; Hansel, A. ; Hunter, J. F. ; Cross, E. S. ; Kroll, J. H. ; Peng, Z. ; Brune, William Henry ; Jimenez, J. L. / In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor. In: Atmospheric Chemistry and Physics Discussions. 2015 ; Vol. 15, No. 21. pp. 30409-30471.
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abstract = "Ambient air was oxidized by OH radicals in an oxidation flow reactor (OFR) located in a montane pine forest during the BEACHON-RoMBAS campaign to study biogenic secondary organic aerosol (SOA) formation and aging. High OH concentrations and short residence times allowed for semi-continuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative time scales of condensation of low volatility organic compounds (LVOCs) onto particles, condensational loss to the walls, and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 4 μg m-3 when LVOC fate corrected) compared to daytime (average 1 μg m-3 when LVOC fate corrected), with maximum formation observed at 0.4-1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene + p-cymene concentrations, including a substantial increase just after sunrise at 07:00 LT. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 6 times more SOA was formed in the reactor from OH oxidation than could be explained by the VOCs measured in ambient air. Several recently-developed instruments quantified ambient semi- and intermediate-volatility organic compounds (S/IVOCs) that were not detected by a PTR-TOF-MS. An SOA yield of 24-80 {\%} from those compounds can explain the observed SOA, suggesting that these typically unmeasured S/IVOCs play a substantial role in ambient SOA formation. Our results allow ruling out condensation sticking coefficients much lower than 1. Our measurements help clarify the magnitude of SOA formation in forested environments, and demonstrate methods for interpretation of ambient OFR measurements.",
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Palm, BB, Campuzano-Jost, P, Ortega, AM, Day, DA, Kaser, L, Jud, W, Karl, T, Hansel, A, Hunter, JF, Cross, ES, Kroll, JH, Peng, Z, Brune, WH & Jimenez, JL 2015, 'In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor', Atmospheric Chemistry and Physics Discussions, vol. 15, no. 21, pp. 30409-30471. https://doi.org/10.5194/acpd-15-30409-2015

In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor. / Palm, B. B.; Campuzano-Jost, P.; Ortega, A. M.; Day, D. A.; Kaser, L.; Jud, W.; Karl, T.; Hansel, A.; Hunter, J. F.; Cross, E. S.; Kroll, J. H.; Peng, Z.; Brune, William Henry; Jimenez, J. L.

In: Atmospheric Chemistry and Physics Discussions, Vol. 15, No. 21, 04.11.2015, p. 30409-30471.

Research output: Contribution to journalArticle

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T1 - In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

AU - Palm, B. B.

AU - Campuzano-Jost, P.

AU - Ortega, A. M.

AU - Day, D. A.

AU - Kaser, L.

AU - Jud, W.

AU - Karl, T.

AU - Hansel, A.

AU - Hunter, J. F.

AU - Cross, E. S.

AU - Kroll, J. H.

AU - Peng, Z.

AU - Brune, William Henry

AU - Jimenez, J. L.

PY - 2015/11/4

Y1 - 2015/11/4

N2 - Ambient air was oxidized by OH radicals in an oxidation flow reactor (OFR) located in a montane pine forest during the BEACHON-RoMBAS campaign to study biogenic secondary organic aerosol (SOA) formation and aging. High OH concentrations and short residence times allowed for semi-continuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative time scales of condensation of low volatility organic compounds (LVOCs) onto particles, condensational loss to the walls, and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 4 μg m-3 when LVOC fate corrected) compared to daytime (average 1 μg m-3 when LVOC fate corrected), with maximum formation observed at 0.4-1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene + p-cymene concentrations, including a substantial increase just after sunrise at 07:00 LT. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic compounds, and net production at lower ages followed by net consumption of terpenoid oxidation products as photochemical age increased. New particle formation was observed in the reactor after oxidation, especially during times when precursor gas concentrations and SOA formation were largest. Approximately 6 times more SOA was formed in the reactor from OH oxidation than could be explained by the VOCs measured in ambient air. Several recently-developed instruments quantified ambient semi- and intermediate-volatility organic compounds (S/IVOCs) that were not detected by a PTR-TOF-MS. An SOA yield of 24-80 % from those compounds can explain the observed SOA, suggesting that these typically unmeasured S/IVOCs play a substantial role in ambient SOA formation. Our results allow ruling out condensation sticking coefficients much lower than 1. Our measurements help clarify the magnitude of SOA formation in forested environments, and demonstrate methods for interpretation of ambient OFR measurements.

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