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Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
doi:10.5194/acp-2017-249
© Author(s) 2017. This work is distributed
under the Creative Commons Attribution 3.0 License.
Research article
27 Mar 2017
Review status
This discussion paper is under review for the journal Atmospheric Chemistry and Physics (ACP).
Nitrate radical oxidation of γ-terpinene: hydroxy nitrate, total organic nitrate, and secondary organic aerosol yields
Jonathan H. Slade1, Chloé de Perre2, Linda Lee2, and Paul B. Shepson1,3 1Department of Chemistry, Purdue University, West Lafayette, IN 47907
2Department of Agronomy, Purdue University, West Lafayette, IN 47907
3Department of Earth, Atmospheric, and Planetary Sciences, Purdue University, West Lafayette, IN 47907
Abstract. Polyolefinic monoterpenes represent a potentially important but understudied source of organic nitrates (ON) and secondary organic aerosol (SOA) following oxidation due to their high reactivity and propensity for multi-stage chemistry. Recent modeling work suggests that the oxidation of polyolefinic γ-terpinene can be the dominant source of nighttime ON in a mixed forest environment. However, the ON yields, aerosol partitioning behavior, and SOA yields from γ-terpinene oxidation by the nitrate radical (NO3), an important nighttime oxidant, have not been determined experimentally. In this work, we present a comprehensive experimental investigation of the total (gas + particle) ON, hydroxy nitrate, and SOA yields following γ-terpinene oxidation by NO3. Under dry conditions, the hydroxy nitrate yield = 4(+1/−3) %, total ON yield = 14(+3/−2) %, and SOA yield ≤10% under atmospherically-relevant particle mass loadings, similar to those for α-pinene + NO3. Using a chemical box model, we show that the measured concentrations of NO2 and γ-terpinene hydroxy nitrates can be reliably simulated from α-pinene + NO3 chemistry. This suggests that NO3 addition to either of the two internal double bonds of γ-terpinene primarily decomposes forming a relatively volatile keto–aldehyde, reconciling the small SOA yield observed here and for other internal olefinic terpenes. Based on aerosol partitioning analysis and identification of speciated particle-phase ON applying high-resolution liquid chromatography–mass spectrometry, we estimate that a significant fraction of the particle-phase ON has the hydroxy nitrate moiety. This work greatly contributes to our understanding of ON and SOA formation from polyolefin monoterpene oxidation, which could be important in the northern continental U.S. and Midwest, where polyolefinic monoterpene emissions are greatest.

Citation: Slade, J. H., de Perre, C., Lee, L., and Shepson, P. B.: Nitrate radical oxidation of γ-terpinene: hydroxy nitrate, total organic nitrate, and secondary organic aerosol yields, Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2017-249, in review, 2017.
Jonathan H. Slade et al.
Jonathan H. Slade et al.
Jonathan H. Slade et al.

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Short summary
This study provides new insight into the oxidation of polyolefinic monoterpenes and the dependence of hydrocarbon structure on the formation and yields of organic nitrates (ON) and secondary organic aerosol (SOA). Here we have elucidated the ON, hydroxy nitrate, and SOA yields from the NO3 oxidation of γ-terpinene, a potentially relevant nighttime ON precursor in the Midwestern U.S. The results advance our understanding of the chemistry that influences NOx, O3 production, and aerosol formation.
This study provides new insight into the oxidation of polyolefinic monoterpenes and the...
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