Formation of OH radicals in the gas phase reactions of O3 with a series of terpenes

Atkinson, Roger; Aschmann, Sara M.; Arey, Janet; Shorees, Basima

doi:10.1029/92jd00062

Cited by 358 publications

(373 citation statements)

References 61 publications

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“…The concentration of nitrate increased rapidly at the beginning of the reaction and reached a maximum after ∼1 h. During the first 2 h of reaction, TMB and NO decayed exponentially (Figure 3c and d), suggesting that the majority of ON molecules were formed within 2 h of the start of the reaction. Decay rates of TMB and NO for dry and humid experiments were similar (except for the lower decay rates observed on 28 March with RH of ∼85%, for which the reason is not clear), which is consistent with the fact that water vapor has no effects on OH radical formation (Atkinson et al 1992) at the wavelengths of light (centered at 340 nm) employed in this study. In addition, it has been shown that the reaction of RO 2 and NO (reaction (1)) is not affected by RH (Matsunaga and Ziemann, 2009).…”

Section: Resultssupporting

confidence: 72%

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Liu

Shilling

Song

et al. 2012

Aerosol Science and Technology

183

204

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Organonitrate (ON) groups are thought to be important substituents in secondary organic aerosols (SOAs). Model simulations and laboratory studies indicate a large fraction of ON groups in aerosol particles, but much lower quantities are observed in the atmosphere. Hydrolysis of ON groups in aerosol particles has been proposed recently to account for this discrepancy. To test this hypothesis, we simulated formation of ON molecules in a reaction chamber under a wide range of relative humidity (RH) (0 to 90%). The mass fraction of ON groups (5 to 20% for high-NO x experiments) consistently decreased with increasing RH, which was best explained by hydrolysis of ON groups at a rate of 4 day −1 (lifetime of 6 h) for reactions under RH greater than 20%. In addition, we found that secondary nitrogen-containing molecules absorb light, with greater absorption under dry and high-NO x conditions. This work provides the first evidence for particle-phase hydrolysis of ON groups, a process that could substantially reduce ON group concentration in atmospheric SOAs.

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Section: Resultssupporting

confidence: 72%

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Liu

Shilling

Song

et al. 2012

Aerosol Science and Technology

183

204

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“…Similar to that observed for the ozonolysis of α-pinene, the observed interference measured with the addition of C 3 F 6 accounted for approximately 40 % of the observed signal in the absence of C 3 F 6 . When the measured interference was subtracted from the overall signal, the measured OH concentrations results in an overall OH yield of approximately 0.40 ± 0.01, which is in good agreement with the value reported by Atkinson et al (1992) of 0.35 ± 0.05. The percentage of interference as well as the resulting OH yield was relatively constant for each β-pinene concentration used; however, the results suggest that the OH yield may increase with increasing concentrations of β-pinene.…”

Section: Ozonolysis Experimentssupporting

confidence: 78%

Measurements of a potential interference with laser-induced fluorescence measurements of ambient OH from the ozonolysis of biogenic alkenes

Rickly

Stevens

2018

Atmos. Meas. Tech.

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Abstract. Reactions of the hydroxyl radical (OH) play a central role in the chemistry of the atmosphere, and measurements of its concentration can provide a rigorous test of our understanding of atmospheric oxidation. Several recent studies have shown large discrepancies between measured and modeled OH concentrations in forested areas impacted by emissions of biogenic volatile organic compounds (BVOCs), where modeled concentrations were significantly lower than measurements. A potential reason for some of these discrepancies involves interferences associated with the measurement of OH using the laser-induced fluorescencefluorescence assay by gas expansion (LIF-FAGE) technique in these environments. In this study, a turbulent flow reactor operating at atmospheric pressure was coupled to a LIF-FAGE cell and the OH signal produced from the ozonolysis of α-pinene, β-pinene, ocimene, isoprene, and 2-methyl-3-buten-2-ol (MBO) was measured. To distinguish between OH produced from the ozonolysis reactions and any OH artifact produced inside the LIF-FAGE cell, an external chemical scrubbing technique was used, allowing for the direct measurement of any interference. An interference under high ozone (between 2 × 10 13 and 10 × 10 13 cm −3 ) and BVOC concentrations (between approximately 0.1 × 10 12 and 40 × 10 12 cm −3 ) was observed that was not laser generated and was independent of the ozonolysis reaction time. For the ozonolysis of α-and β-pinene, the observed interference accounted for approximately 40 % of the total OH signal, while for the ozonolysis of ocimene the observed interference accounted for approximately 70 % of the total OH signal. Addition of acetic acid to the reactor eliminated the interference, suggesting that the source of the interference in these experiments involved the decomposition of stabilized Criegee intermediates (SCIs) inside the FAGE detection cell. Extrapolation of these measurements to ambient concentrations suggests that these interferences should be below the detection limit of the instrument.

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“…That study used OH yields for β-caryophyllene (6%), which are at the low end of the reported range for OH yields from sesquiterpenes (e.g. Atkinson et al, 1992;Shu and Atkinson, 1994). Our observations suggest the OH yields are much higher, and that enhanced within-canopy reactivity might be a general characteristic of pine forests and other ecosystems where very reactive terpene emissions are substantial.…”

Section: Discussionmentioning

confidence: 98%

Observations of HNO3, ΣAN, ΣPN and NO2 fluxes: evidence for rapid HOx chemistry within a pine forest canopy

2008

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Abstract. Measurements of exchange of reactive nitrogen oxides between the atmosphere and a ponderosa pine forest in the Sierra Nevada Mountains are reported. During winter, we observe upward fluxes of NO 2 , and downward fluxes of total peroxy and peroxy acyl nitrates ( PNs), total gas and particle phase alkyl and multifunctional alkyl nitrates ( ANs (g+p) ), and the sum of gaseous HNO 3 and semi-volatile NO − 3 particles (HNO 3(g+p) ). We use calculations of the vertical profile and flux of NO, partially constrained by observations, to show that net midday NO yi fluxes in winter are -4.9 ppt m s −1 . The signs and magnitudes of these wintertime individual and NO yi fluxes are in the range of prior measurements. In contrast, during summer, we observe downward fluxes only of ANs (g+p) , and upward fluxes of HNO 3(g+p) , PNs and NO 2 with signs and magnitudes that are unlike most, if not all, previous observations and analyses of fluxes of individual nitrogen oxides. The results imply that the mechanisms contributing to NO y fluxes, at least at this site, are much more complex than previously recognized. We show that the observations of upward fluxes of HNO 3(g+p) and PNs during summer are consistent with oxidation of NO 2 and acetaldehyde by an OH x residence time of 1.1×10 10 molec OH cm −3 s, corresponding to 3 to 16×10 7 molecules cm −3 OH within the forest canopy for a 420 to 70 s canopy residence time. We show that AN (g+p) fluxes are consistent with this range in OH if the reaction of OH with ANs produces either HNO 3 or NO 2 with a 6-30% yield. Calculations of NO fluxes constrained by the NO 2 observations and the inferred OH indicate that NO x fluxes are downward into the canopy because of the substantial converCorrespondence to: R. C. Cohen (rccohen@berkeley.edu) sion of NO x to HNO 3 and PNs in the canopy. Even so, we derive that NO x emission fluxes of ∼15 ng(N) m −2 s −1 at midday during summer are required to balance the NO x and NO y flux budgets. These fluxes are partly explained by estimates of soil emissions (estimated to be between 3 and 6 ng(N) m −2 s −1 ). One possibility for the remainder of the NO x source is large HONO emissions. Alternatively, the 15 ng(N) m −2 s −1 emission estimate may be too large, and the budget balanced if the deposition of HNO 3 and PNs is slower than we estimate, if there are large errors in either our understanding of peroxy radical chemistry, or our assumptions that the budget is required to balance because the fluxes do not obey similarity theory.

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Formation of OH radicals in the gas phase reactions of O₃ with a series of terpenes

Cited by 358 publications

References 61 publications

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Measurements of a potential interference with laser-induced fluorescence measurements of ambient OH from the ozonolysis of biogenic alkenes

Observations of HNO<sub>3</sub>, ΣAN, ΣPN and NO<sub>2</sub> fluxes: evidence for rapid HO<sub>x</sub> chemistry within a pine forest canopy

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Formation of OH radicals in the gas phase reactions of O3 with a series of terpenes

Cited by 358 publications

References 61 publications

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Measurements of a potential interference with laser-induced fluorescence measurements of ambient OH from the ozonolysis of biogenic alkenes

Observations of HNO&lt;sub&gt;3&lt;/sub&gt;, ΣAN, ΣPN and NO&lt;sub&gt;2&lt;/sub&gt; fluxes: evidence for rapid HO&lt;sub&gt;x&lt;/sub&gt; chemistry within a pine forest canopy

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Formation of OH radicals in the gas phase reactions of O₃ with a series of terpenes

Observations of HNO<sub>3</sub>, ΣAN, ΣPN and NO<sub>2</sub> fluxes: evidence for rapid HO<sub>x</sub> chemistry within a pine forest canopy