Product study and mechanisms of the reactions of α‐pinene and of pinonaldehyde with OH radicals

Nozière, Barbara; Barnes, Ian; Becker, Karl‐Heinz

doi:10.1029/1999jd900778

Cited by 177 publications

(231 citation statements)

References 35 publications

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“…These values are in agreement with previously reported yields of total organic nitrates from high-NO x photooxidation of e.g. α-pinene (18 ± 9%) (46). The correspondence between the previously observed and calculated total alkyl nitrate yields, and our calculated contribution of alkyl nitrates to SOA (i.e.…”

Section: Detection Limitsupporting

confidence: 93%

Real Time In Situ Detection of Organic Nitrates in Atmospheric Aerosols

Rollins

Smith

Wilson

et al. 2010

Environ. Sci. Technol.

103

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A novel instrument is described that quantifies total particle phase organic nitrates in real time with a detection limit of 0.11 µg m −3 min −1 , 45 ppt min −1 (-ONO 2 ). Aerosol nitrates are separated from gas phase nitrates with a short residence time activated carbon denuder.Detection of organic molecules containing -ONO 2 subunits is accomplished using thermal dissociation coupled to laser induced fluorescence detection of NO 2 . This instrument is capable of high time resolution (seconds) measurements of particle phase organic nitrates, without interference from inorganic nitrate. Here we use it to quantify organic nitrates in secondary organic aerosol generated from high-NO x photooxidation of limonene, α-pinene, ∆-3-carene, and tridecane. In these experiments the organic nitrate moiety is observed to be 6-15% of the total SOA mass.

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Section: Detection Limitsupporting

confidence: 93%

Real Time In Situ Detection of Organic Nitrates in Atmospheric Aerosols

Rollins

Smith

Wilson

et al. 2010

Environ. Sci. Technol.

103

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“…Values can be extrapolated to carbon numbers below C 14 by using the approach presented previously (11). For example, the sum of the yields of secondary and tertiary β-HN predicted for the reaction of α-pinene is 0.22, in reasonable agreement with a measured total organic nitrate yield of 0.18 AE 0.09 (19). We have shown previously for reactions of linear alkenes (20) that yields of β-HN, DHN, and carbonyls can be used with structure-reactivity relationships to develop a complete reaction mechanism that can be used with gas-particle partitioning theory to model SOA formation.…”

Section: Discussionmentioning

confidence: 66%

Yields ofβ-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates formed from OH radical-initiated reactions of 2-methyl-1-alkenes

Matsunaga

Ziemann

2009

Proc. Natl. Acad. Sci. U.S.A.

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Yields of β-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates, in particles formed from OH radical-initiated reactions of C 9 -C 15 2-methyl-1-alkenes in the presence of NO x were measured by using a thermal desorption particle beam mass spectrometer coupled to a high-performance liquid chromatograph with a UVvisible (UV-vis) detector. Yields of β-hydroxynitrates and dihydroxynitrates increased with carbon number primarily due to enhanced gas-to-particle partitioning before reaching plateaus at ≈C 14 -C 15 , where the compounds were essentially entirely in the particle phase. Plateau yields of β-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates were 0.183 AE 0.005, 0.045 AE 0.005, and 0.034AE 0.005, and, after normalization for OH radical addition to the C ¼ C double bond, were 0.225 AE 0.007, 0.055 AE 0.006, and 0.042 AE 0.006. The fractions of 1-hydroxy and 2-hydroxy β-hydroxynitrate isomers were 0.90∕0.10. Yields measured here and in our previous study of reactions of linear internal alkenes and linear 1-alkenes indicate that, for these alkene classes, the relative branching ratios for forming tertiary, secondary, and primary β-hydroxyalkyl radicals by OH radical addition to the C ¼ C double bond are 4.3∕1.9∕1.0, and the branching ratios for forming β-hydroxynitrates from reactions of tertiary, secondary, and primary β-hydroxyperoxy radicals with NO are 0.25, 0.15, and 0.12. The effects of H 2 O vapor and NH 3 on yields were also explored.aerosol | atmospheric chemistry | organice nitrate | particles H ydrocarbons are emitted to the atmosphere from anthropogenic and biogenic sources. Globally, more than half are biogenic alkenes including isoprene (C 5 ), monoterpenes (C 10 ), and sesquiterpenes (C 15 ) (1). These compounds have a variety of linear, branched, and cyclic structures containing one or more C ¼ C double bonds and in the atmosphere react with OH radicals, O 3 , and NO 3 radicals to form oxidized products (2, 3). In urban and polluted rural areas where peroxy radical intermediates react primarily with NO (4), one important class of products is organic nitrates (2, 3). For example, hydroxynitrates formed from OH radical-initiated reactions of isoprene have been identified in urban air (5) and impact O 3 formation and NO x removal (6) as well as secondary organic aerosol (SOA) formation (7). It has been estimated that, globally, about two-thirds of hydroxyperoxy radicals formed from isoprene oxidation react with NO (8), a value that probably applies to other terpenes.In spite of their atmospheric importance, little is known about the chemistry of hydroxynitrates. This is primarily because of a lack of analytical methods and reference compounds (5, 9). In a recent study, Paulot et al. (10) employed chemical ionization mass spectrometry to monitor hydroxynitrates formed during isoprene photooxidation, and then used this information to help constrain a detailed chemical mechanism. Even here, however, significant uncertainties exist because many hydroxynitrate isomers could not be disti...

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“…The chemical compositions of the SOAs generated during ozonolysis and photooxidation should be somewhat different from each other, according to the literature (Jang and Kamens 1999;Iinuma et al 2004Iinuma et al , 2005Ma et al 2008;Shilling et al 2009;Noziere et al 1999;Ng et al 2007;Claeys et al 2009;Eddingsaas et al 2012). In the present study, a non-negligible value of nitrate to organic (HRNO 3 /HROrg) ratio, which was calculated from the H-ToF-AMS data, and slightly larger O/C and H/C ratios were observed for the SOAs generated by photooxidation (Table 1) compared to those for the SOAs generated by ozonolysis.…”

Section: Resultsmentioning

confidence: 99%

Wavelength Dependence of Refractive Index of Secondary Organic Aerosols Generated during the Ozonolysis and Photooxidation of α-Pinene

Nakayama

Sato

Matsumi

et al. 2012

SOLA

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Atmospheric aerosol particles play an important role in climate change by scattering and absorbing solar radiation. To quantify the direct influence of aerosols on the atmospheric radiation balance, a detailed understanding of the complex refractive index (RI) for a variety of aerosols is required. The wavelength dependence of the RI values for secondary organic aerosols (SOAs) generated during the ozonolysis and photooxidation of α-pinene, which is a major biogenic volatile organic compound (BVOC), was investigated using a photoacoustic soot spectrometer (PASS) and a cavity ring-down spectrometer (CRDS). The real part of the RI values for SOAs generated from both ozonolysis and photooxidation was found to lie between 1.4 and 1.5 at 405, 532, and 781 nm, and to slightly increase with decreasing wavelength. Additionally, the imaginary part of the RI values for these SOAs was found to be negligible (< 0.003) at all of the wavelengths studied (405, 532, and 781 nm). The obtained complex RI values were also compared with values reported in the literature and the chemical properties of the SOAs, which were measured using a high resolution time-of-flight aerosol mass spectrometer (H-ToF-AMS).

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Product study and mechanisms of the reactions of α‐pinene and of pinonaldehyde with OH radicals

Cited by 177 publications

References 35 publications

Real Time In Situ Detection of Organic Nitrates in Atmospheric Aerosols

Real Time In Situ Detection of Organic Nitrates in Atmospheric Aerosols

Yields ofβ-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates formed from OH radical-initiated reactions of 2-methyl-1-alkenes

Wavelength Dependence of Refractive Index of Secondary Organic Aerosols Generated during the Ozonolysis and Photooxidation of α-Pinene

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