Aerosol-chamber study of the α-pinene/O3 reaction: influence of particle acidity on aerosol yields and products

Iinuma, Yoshiteru; Böge, Olaf; Gnauk, T.; Herrmann, Hartmut

doi:10.1016/j.atmosenv.2003.10.015

Cited by 319 publications

(338 citation statements)

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“…The results of this work concerning these coefficients may contribute to the understanding of enhanced aerosol yields obtained with acidic particle seeds in recent smog chamber studies. [1][2][3][4][5] The comparison of H MVK and H MACR measured in this work leads to key questions concerning the processes responsible for the increase of these coefficients at high acidity: (i) Why do the Henry's law coefficients for MVK and MACR display such vastly different behavior with acidity? (ii) Why is the variation with acidity for MVK similar to the values reported previously for other carbonyl compounds and alcohols?…”

Section: Discussionmentioning

confidence: 99%

“…Recent studies have shown that the interactions of oxygenated organic compounds with acidic particles might play a role in the formation of secondary organic aerosols, [1][2][3][4][5] in particular, for precursors for which gas-phase oxidation does not otherwise produce aerosols, such as isoprene and its oxidation products. 4 Various explanations for these observations have been proposed, most emphasizing that the increase of aerosol mass was due to the formation of large molecular weight compounds by acidcatalyzed reactions.…”

Section: Introductionmentioning

confidence: 99%

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The Uptake of Methyl Vinyl Ketone, Methacrolein, and 2-Methyl-3-butene-2-ol onto Sulfuric Acid Solutions

et al. 2006

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To investigate the link between molecular structure, reactivity, and partitioning of oxygenated organic compounds in acidic aerosols, the uptake of three compounds found in the atmosphere, methyl vinyl ketone (MVK), methacrolein (MACR), and 2-methyl-3-butene-2-ol (MBO), by sulfuric acid solutions has been measured using a rotated wetted-wall reactor (RWW) coupled to a chemical ionization mass spectrometer (CIMS). MVK was found to partition reversibly into 20-75 wt % H 2 SO 4 solutions, and we report Henry's law coefficients between 20 and 7000 M atm -1 over this range. A chemical reaction for MVK was likely responsible for the uptake observed for 80-96 wt % H 2 SO 4 solutions. We derive an upper limit to the aldol self-reaction rate coefficient for MVK in 80 wt % solution of ∼3 M -1 s -1 . MACR partitioned reversibly over most of the acidity range, and in contrast to that for MVK, the Henry's law coefficient was relatively independent of H 2 SO 4 content. These differences indicate that the increase of the coefficient with acidity is likely due to the ability of the carbonyl molecule to form an enol. These results indicate that aldol condensation can be facile in concentrated sulfuric acid solutions, but it should be negligibly slow in dilute acid solutions such as tropospheric aerosols. MBO uptake could be explained by a Henry's law coefficient that decreases slightly as acid content varies from 20 to 55 wt % H 2 SO 4 ; we also measured the value in water, 70 M atm -1 at 298 K. A steady-state uptake of MBO was observed onto 40-80 wt % H 2 SO 4 solutions, a reaction product was observed, and the reaction was tentatively identified as Pinacol rearrangement. Similar rearrangements could be at the origin of some substituted oxygenated species found in atmospheric aerosols.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Uptake of Methyl Vinyl Ketone, Methacrolein, and 2-Methyl-3-butene-2-ol onto Sulfuric Acid Solutions

et al. 2006

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“…Gao et al (2004) assigned the MW 358 α-pinene/O 3 compound to a dehydration product formed between the gem-diol forms of two norpinonic acid molecules. Iinuma et al (2004) reported MW 354 and 370 α-pinene/O 3 products that were enhanced in acidic conditions and tentatively assigned them to reaction products between the gem-diol of pinonaldehyde and pinonaldehyde, and between pinonaldehyde and hydroxypinonaldehyde, respectively. Docherty et al (2005) proposed peroxycarboxylic acid dimers for the structure of higher-MW SOA products from the ozonolysis of α-pinene in which peroxypinic acid and the gem-diol of a keto or aldehydic compound are connected via a peroxy bridge.…”

Section: Introductionmentioning

confidence: 99%

High-molecular-weight esters in <i>α</i>-pinene ozonolysis secondary organic aerosol: structural characterization and mechanistic proposal for their formation from highly oxygenated molecules

et al. 2018

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Abstract. Stable high-molecular-weight esters are present in α-pinene ozonolysis secondary organic aerosol (SOA) with the two most abundant ones corresponding to a hydroxypinonyl ester of cis-pinic acid with a molecular weight (MW) of 368 (C 19 H 28 O 7 ) and a diaterpenylic ester of cis-pinic acid with a MW of 358 (C 17 H 26 O 8 ). However, their molecular structures are not completely elucidated and their relationship with highly oxygenated molecules (HOMs) in the gas phase is still unclear. In this study, liquid chromatography in combination with positive ion electrospray ionization mass spectrometry has been performed on highmolecular-weight esters present in α-pinene ozonolysis SOA with and without derivatization into methyl esters. Unambiguous evidence could be obtained for the molecular structure of the MW 368 ester in that it corresponds to an ester of cis-pinic acid where the carboxyl substituent of the dimethylcyclobutane ring and not the methylcarboxyl substituent is esterified with 7-hydroxypinonic acid. The same linkage was already proposed in previous work for the MW 358 ester (Yasmeen et al., 2010), but could be supported in the present study. Guided by the molecular structures of these stable esters, we propose a formation mechanism from gas-phase HOMs that takes into account the formation of an unstable C 19 H 28 O 11 product, which is detected as a major species in α-pinene ozonolysis experiments as well as in the pristine forest atmosphere by chemical ionization-atmospheric pressure ionization-time-of-flight mass spectrometry with nitrate clustering (Ehn et al., 2012. It is suggested that an acyl peroxy radical related to cis-pinic acid (RO 2 q ) and an alkoxy radical related to 7-or 5-hydroxypinonic acid (R O q ) serve as key gas-phase radicals and combine according to a RO 2 + R O q → RO 3 R radical termination reaction. Subsequently, the unstable C 19 H 28 O 11 HOM species decompose through the loss of oxygen or ketene from the inner part containing a labile trioxide function and the conversion of the unstable acyl hydroperoxide groups to carboxyl groups, resulting in stable esters with a molecular composition of C 19 H 28 O 7 (MW 368) and C 17 H 26 O 8 (MW 358), respectively. The proposed mechanism is supported by several observations reported in the literature. On the basis of the indirect evidence presented in this study, we hypothesize that RO 2 + R O q → RO 3 R chemistry is at the underlying molecular basis of high-molecular-weight ester formation upon α-pinene ozonolysis and may thus be of importance for new particle formation and growth in pristine forested environments.

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“…Previous laboratory studies have found increased organic mass incorporated into acidic solutions as compared to non-acidic solutions for various gaseous aldehydes (Iraci and Tolbert, 1997;Jang and Kamens, 2001;Jang et al, 2003aJang et al, , b, 2002Michelsen et al, 2004;Liggio et al, 2005;Zhao et al, 2005); ketones (Jang et al, 2003a, b;Noziere and Riemer, 2003); oxidation products of isoprene, acrolein and a-pinene (Czoschke et al, 2003;Iinuma et al, 2004;Tolocka et al, 2004); and isoprene itself (Limbeck et al, 2003). Many studies have suggested that in order for the organic vapors to be incorporated into the aerosol, oligomerization or polymerization must occur (Jang and Kamens, 2001;Czoschke et al, 2003;Jang et al, 2003aJang et al, , b, 2002Jang et al, , 2005Kalberer et al, 2004;Tolocka et al, 2004;Noziere and Esteve, 2005).…”

Section: Introductionmentioning

confidence: 99%

“…Gas chromatography techniques have also been used in identifying specific reaction products (Jang et al, 2003a, b;Noziere and Riemer, 2003), however not all acidcatalyzed reaction products are stable in a GC column; thus gas chromatography cannot solely be used to identify products. Various mass spectrometry techniques have also been used to show evidence of polymerization and identify the reaction products (Iinuma et al, 2004;Kalberer et al, 2004;Tolocka et al, 2004;Liggio et al, 2005). However, identifying reaction products via these techniques is not trivial as fragmentation often creates complicated spectra.…”

Section: Introductionmentioning

confidence: 99%

Acid-catalyzed reactions of hexanal on sulfuric acid particles: Identification of reaction products

Garland

Elrod

Kincaid

et al. 2006

Atmospheric Environment

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While it is well established that organics compose a large fraction of the atmospheric aerosol mass, the mechanisms through which organics are incorporated into atmospheric aerosols are not well understood. Acid-catalyzed reactions of compounds with carbonyl groups have recently been suggested as important pathways for transfer of volatile organics into acidic aerosols. In the present study, we use the aerodyne aerosol mass spectrometer (AMS) to probe the uptake of gasphase hexanal into ammonium sulfate and sulfuric acid aerosols. While both deliquesced and dry non-acidic ammonium sulfate aerosols showed no organic uptake, the acidic aerosols took up substantial amounts of organic material when exposed to hexanal vapor. Further, we used 1 H-NMR, Fourier transform infrared (FTIR) spectroscopy and GC-MS to identify the products of the acid-catalyzed reaction of hexanal in acidic aerosols. Both aldol condensation and hemiacetal products were identified, with the dominant reaction products dependent upon the initial acid concentration of the aerosol. The aldol condensation product was formed only at initial concentrations of 75-96 wt% sulfuric acid in water. The hemiacetal was produced at all sulfuric acid concentrations studied, 30-96 wt% sulfuric acid in water. Aerosols up to 88.4 wt% organic/11.1 wt% H 2 SO 4 /0.5 wt% water were produced via these two dimerization reaction pathways. The UV-VIS spectrum of the isolated aldol condensation product, 2-butyl 2-octenal, extends into the visible region, suggesting these reactions may impact aerosol optical properties as well as aerosol composition. In contrast to previous suggestions, no polymerization of hexanal or its products was observed at any sulfuric acid concentration studied, from 30 to 96 wt% in water. r

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Aerosol-chamber study of the α-pinene/O3 reaction: influence of particle acidity on aerosol yields and products

Cited by 319 publications

References 46 publications

The Uptake of Methyl Vinyl Ketone, Methacrolein, and 2-Methyl-3-butene-2-ol onto Sulfuric Acid Solutions

The Uptake of Methyl Vinyl Ketone, Methacrolein, and 2-Methyl-3-butene-2-ol onto Sulfuric Acid Solutions

High-molecular-weight esters in <i>α</i>-pinene ozonolysis secondary organic aerosol: structural characterization and mechanistic proposal for their formation from highly oxygenated molecules

Acid-catalyzed reactions of hexanal on sulfuric acid particles: Identification of reaction products

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Aerosol-chamber study of the α-pinene/O3 reaction: influence of particle acidity on aerosol yields and products

Cited by 319 publications

References 46 publications

The Uptake of Methyl Vinyl Ketone, Methacrolein, and 2-Methyl-3-butene-2-ol onto Sulfuric Acid Solutions

The Uptake of Methyl Vinyl Ketone, Methacrolein, and 2-Methyl-3-butene-2-ol onto Sulfuric Acid Solutions

High-molecular-weight esters in &lt;i&gt;α&lt;/i&gt;-pinene ozonolysis secondary organic aerosol: structural characterization and mechanistic proposal for their formation from highly oxygenated molecules

Acid-catalyzed reactions of hexanal on sulfuric acid particles: Identification of reaction products

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High-molecular-weight esters in <i>α</i>-pinene ozonolysis secondary organic aerosol: structural characterization and mechanistic proposal for their formation from highly oxygenated molecules