Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents

Kahnt, Ariane; Iinuma, Yoshiteru; Mutzel, Anke; Böge, Olaf; Claeys, Magda; Herrmann, Hartmut

doi:10.5194/acp-14-719-2014

Cited by 29 publications

(47 citation statements)

References 59 publications

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“…Their analysis showed two structurally different carboxylic acid species -a hydroxyl-acidic ester as well as a peroxyacetyl carboxylic acid. It is also of interest that one recurring molecular formula in all OH/NO x samples is that of C 9 H 13 O 7 N. Assuming that it is a nitric acid ester (ROH + HONO 2 → RONO 2 + H 2 O), the unesterified compound would have the formula C 9 H 14 O 5 , a compound observed in APIN, BPIN, HUM, MYR, and TMB OH/NO x samples in this study as well as in ozonolysis of alpha-pinene, 68 limonene, 69,70 campholenic aldehyde 65 in previous studies. It is not clear how the C 9 H 13 O 7 N could be formed from the aromatic precursors; however, we cannot exclude the possibility that its occurrence in all samples is an experimental artifact from "carry-over" between SOA generated from different precursors on different days.…”

Section: Resultsmentioning

confidence: 99%

“…62 Another molecular formula, C 9 H 14 O 3 , identified as ketolimononaldehyde in limonene SOA, 63 is also appearing in all the O 3 samples. Other common formulas observed in all O 3 and all OH/NO x samples include C 10 H 14 O 5 , possibly peroxo-pinic acid or its isomer, 64 previously observed in α-pinene ozonolysis as well as campholenic aldehyde ozonolysis, 65 and C 10 H 16 O 6 , which has been potentially identified as an ester of glutaric acid or 5-hydroxy-pentanoic acid as seen in the study of ozonolysis of cyclohexene by Hamilton et al 66 A study of the ozonolysis of α-pinene and limonene by Warscheid and Hoffmann 67 also identified the molecular formula of C 10 H 16 O 6 through an online MS n technique. Their analysis showed two structurally different carboxylic acid species -a hydroxyl-acidic ester as well as a peroxyacetyl carboxylic acid.…”

Section: Resultsmentioning

confidence: 99%

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Molecular Characterization of Organosulfates in Organic Aerosols from Shanghai and Los Angeles Urban Areas by Nanospray-Desorption Electrospray Ionization High-Resolution Mass Spectrometry

Tao

Levac

et al. 2014

Environ. Sci. Technol.

151

219

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This work presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, Dlimonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NO x (to simulate an urban atmosphere). Chamber-and flow-tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3−8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NO x -generated SOA had more unique visual appearance and indicated a lower extent of product overlap. Furthermore, the fraction of nitrogen-containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NO x oxidation conditions compared to the ozone-driven oxidation. Comparison of the SOA constituents before and after photolysis showed the tendency to reduce the average number of atoms in the SOA compounds without a significant effect on the overall O/C and H/C ratios. SOA prepared by OH/NO x photooxidation of 1,3,5-trimethylbenzene and guaiacol were more resilient to photolysis despite being the most light-absorbing. The composition of SOA prepared by ozonolysis of monoterpenes changed more significantly as a result of the photolysis. The results indicate that aqueous photolysis of dissolved SOA compounds in cloud/fog water can occur in various types of SOA, and on atmospherically relevant time scales. However, the extent of the photolysis-driven change in molecular composition depends on the specific type of SOA.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Molecular Characterization of Organosulfates in Organic Aerosols from Shanghai and Los Angeles Urban Areas by Nanospray-Desorption Electrospray Ionization High-Resolution Mass Spectrometry

Tao

Levac

et al. 2014

Environ. Sci. Technol.

151

219

View full text Add to dashboard Cite

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“…As discussed previously, MBTCA and terebic acid will be formed from the OH-initiated oxidation of pinonic acid and terpenylic acid, respectively. Kahnt et al (2014) suggested that C 9 H 14 O 5 as well as C 9 H 14 O 6 formed from the ozonolysis of campholenic aldehyde were C9-carbonyl-dicarboxylic acid and C9-tricarboxylic acid, respectively. As campholenic aldehyde is formed from the heterogeneous oxidation of a-pinene, C9-carbonyl-dicarboxylic acid and C9-tricarboxylic acid will also be formed from the ozonolysis of a-pinene.…”

Section: Time Series and Oh Exposurementioning

confidence: 98%

Terpenylic acid and nine-carbon multifunctional compounds formed during the aging of β-pinene ozonolysis secondary organic aerosol

Sato

Jia

Toko

et al. 2016

Atmospheric Environment

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“…Here the reaction of ozone and α-pinene leads to the formation α-pinene oxide which can rearrange to campholenic aldehyde. Once formed, campholenic aldehyde may undergo further reaction with ozone to form terpenylic aldehyde, which can then be further oxidized in the particle phase to form terpenylic acid (Iinuma et al, 2013;Kahnt et al, 2014).…”

Section: Introductionmentioning

confidence: 99%

Dimers in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity

et al. 2014

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Abstract. The formation of secondary organic aerosol (SOA) from both ozonolysis and hydroxyl radical (OH)-initiated oxidation of α-pinene under conditions of high nitric oxide (NO) concentrations with varying relative humidity (RH) and aerosol acidity was investigated in the University of North Carolina dual outdoor smog chamber facility. SOA formation from ozonolysis of α-pinene was enhanced relative to that from OH-initiated oxidation in the presence of initially high-NO conditions. However, no effect of RH on SOA mass was evident. Ozone (O 3 )-initiated oxidation of α-pinene in the presence of ammonium sulfate (AS) seed coated with organic aerosol from OH-initiated oxidation of α-pinene showed reduced nucleation compared to ozonolysis in the presence of pure AS seed aerosol.The chemical composition of α-pinene SOA was investigated by ultra-performance liquid chromatography/electrospray ionization high-resolution quadrupole timeof-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS), with a focus on the formation of carboxylic acids and highmolecular weight dimers. A total of eight carboxylic acids and four dimers were identified, constituting between 8 and 12 % of the total α-pinene SOA mass. OH-initiated oxidation of α-pinene in the presence of nitrogen oxides (NO x ) resulted in the formation of highly oxidized carboxylic acids, such as 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). The formation of dimers was observed only in SOA produced from the ozonolysis of α-pinene in the absence of NO x , with increased concentrations by a factor of two at higher RH (50-90 %) relative to lower RH (30-50 %). The increased formation of dimers correlates with an observed increase in new particle formation at higher RH due to nucleation. Increased aerosol acidity was found to have a negligible effect on the formation of the dimers. SOA mass yield did not influence the chemical composition of SOA formed from α-pinene ozonolysis with respect to carboxylic acids and dimers.The results support the formation of the high-molecular weight dimers through gas-phase reactions of the stabilized Criegee Intermediate (sCI) formed from the ozonolysis of α-pinene. The high molecular weight and polar nature of dimers formed in the gas phase may explain increased particle number concentration as a result of homogenous nucleation. Since three of these dimers (i.e. pinyl-diaterpenyl dimer (MW 358), pinyl-diaterebyl dimer (MW 344) and pinonyl-pinyl dimer (MW 368)) have been observed in both laboratory-generated and ambient fine organic aerosol samples, we conclude that the dimers observed in this study can be used as tracers for the O 3 -initiated oxidation of α-pinene, and are therefore indicative of enhanced anthropogenic activities, and that the high molecular weight and low volatility dimers result in homogenous nucleation under laboratory conditions, increasing the particle number concentration.

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Campholenic aldehyde ozonolysis: a mechanism leading to specific biogenic secondary organic aerosol constituents

Cited by 29 publications

References 59 publications

Molecular Characterization of Organosulfates in Organic Aerosols from Shanghai and Los Angeles Urban Areas by Nanospray-Desorption Electrospray Ionization High-Resolution Mass Spectrometry

Molecular Characterization of Organosulfates in Organic Aerosols from Shanghai and Los Angeles Urban Areas by Nanospray-Desorption Electrospray Ionization High-Resolution Mass Spectrometry

Terpenylic acid and nine-carbon multifunctional compounds formed during the aging of β-pinene ozonolysis secondary organic aerosol

Dimers in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity

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