Aqueous phase oligomerization of methyl vinyl ketone through photooxidation – Part 2: Development of the chemical mechanism and atmospheric implications

Ervens, B.; Renard, P.; Ravier, Sylvain; Clément, Jean‐Louis; Monod, Anne

doi:10.5194/acpd-14-21565-2014

Cited by 6 publications

(6 citation statements)

References 73 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Currently, the aqueous-phase OH reactivity of dimers is poorly constrained. Ervens et al 25 have reported the OH reactivity of methylvinyl ketone oligomers (1 × 10 8 M −1 s −1 ), obtained by fitting experimental observations in a chemical system in which dimers formed and reacted simultaneously. The strength and novelty of this work lie in the in situ measurement of the decaying dimers that are actually extracted from α-pinene SOA.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…Photochemistry of dimers has not been incorporated into cloudwater chemistry models, with one exception. 25 Analysis of dimers at the molecular level is a prerequisite for understanding their chemistry, whereas for atmospheric modeling, the concept of a generalized OH reactivity 26 that represents the wide diversity of dimers is essential, given that a complete speciation of dimers is infeasible.…”

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Rapid Aqueous-Phase Photooxidation of Dimers in the α-Pinene Secondary Organic Aerosol

Zhao

Aljawhary

Lee

et al. 2017

Environ. Sci. Technol. Lett.

View full text Add to dashboard Cite

Chemical complexity significantly hinders our understanding of the formation and evolution of secondary organic aerosol (SOA), which is known to have impacts on air quality and global climate. Dimeric substances present in SOA comprise a major fraction of extremely low-volatile organic compounds that are especially poorly characterized. Using online mass spectrometry, we have investigated the aqueous-phase OH oxidation of dimers present in the water-soluble fraction of SOA arising from ozonolysis of α-pinene. This study highlights very rapid OH oxidation of dimeric compounds. In particular, using pinonic acid as a reference compound, we obtained second-order rate constants for the loss of 12 dimers, with an average value of (1.3 ± 0.5) × 109 M–1 s–1 at room temperature. For the first time, this study demonstrates that rapid loss of dimeric compounds will occur in cloudwater and potentially also in aqueous aerosols.

show abstract

Section: ■ Materials and Methodsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Rapid Aqueous-Phase Photooxidation of Dimers in the α-Pinene Secondary Organic Aerosol

Zhao

Aljawhary

Lee

et al. 2017

Environ. Sci. Technol. Lett.

View full text Add to dashboard Cite

show abstract

“…Very long homologous series of peaks, with mass ranging up to ∼1500 Da with three or more members and separated by the same repeating unit ("monomer") were detected in all types of experiments, as observed in previous studies of isoprene photooxidation, 15,16 isoprene ozonolysis in a smog chamber, 78 and isoprene, methacrolein, and methyl vinyl ketone bulk aqueous photooxidation. [48][49][50]79,80 Formation of such long oligomers can be explained by high concentrations of VOC precursor used in these experiments. As shown by Kourtchev et al, 41 the formation of oligomers is correlated with the initial precursor concentration (excluding a strong influence from instrumental artifacts and) confirmed by liquid chromatography mass spectrometry (LC-MS) measurements of monoterpene SOA.…”

Section: Resultsmentioning

confidence: 93%

Section: Resultsmentioning

confidence: 99%

“…In this respect, it has been shown in a previous study that dissolved O 2 inhibits radical oligomerization, 48 and water droplets in atmospheric conditions are likely to be saturated with O 2 assuming partitioning equilibrium. 49 In addition, oxidation in the condensed phase is limited by the uptake of •OH from the gas phase. 83 In smog-chamber experiments, 2-hydroxy-2-methylbutanedial (C 5 H 8 O 3 ) 16 is another important monomer making up to 96 (>4 units) homologous series with up to 9 monomer units, producing hemiacetals through addition chemistry, 16 while it is not as important in aqueous-phase oxidation likely due to hydrolysis of hemiacetals.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Cloud Processing of Secondary Organic Aerosol from Isoprene and Methacrolein Photooxidation

et al. 2017

View full text Add to dashboard Cite

Aerosol-cloud interaction contributes to the largest uncertainties in the estimation and interpretation of the Earth’s changing energy budget. The present study explores experimentally the impacts of water condensation-evaporation events, mimicking processes occurring in atmospheric clouds, on the molecular composition of secondary organic aerosol (SOA) from the photooxidation of methacrolein. A range of on- and off-line mass spectrometry techniques were used to obtain a detailed chemical characterization of SOA formed in control experiments in dry conditions, in triphasic experiments simulating gas-particle-cloud droplet interactions (starting from dry conditions and from 60% relative humidity (RH)), and in bulk aqueous-phase experiments. We observed that cloud events trigger fast SOA formation accompanied by evaporative losses. These evaporative losses decreased SOA concentration in the simulation chamber by 25–32% upon RH increase, while aqueous SOA was found to be metastable and slowly evaporated after cloud dissipation. In the simulation chamber, SOA composition measured with a high-resolution time-of-flight aerosol mass spectrometer, did not change during cloud events compared with high RH conditions (RH > 80%). In all experiments, off-line mass spectrometry techniques emphasize the critical role of 2-methylglyceric acid as a major product of isoprene chemistry, as an important contributor to the total SOA mass (15–20%) and as a key building block of oligomers found in the particulate phase. Interestingly, the comparison between the series of oligomers obtained from experiments performed under different conditions show a markedly different reactivity. In particular, long reaction times at high RH seem to create the conditions for aqueous-phase processing to occur in a more efficient manner than during two relatively short cloud events.

show abstract

Aqueous phase oligomerization of α,β-unsaturated carbonyls and acids investigated using ion mobility spectrometry coupled to mass spectrometry (IMS-MS)

Renard

Tlili

Ravier

et al. 2016

Atmospheric Environment

View full text Add to dashboard Cite

One of the current essential issues to unravel our ability to forecast future climate change and air quality, implies a better understanding of natural processes leading of secondary organic aerosol (SOA) formation, and in particular the formation and fate of oligomers. The difficulty in characterizing macromolecules is to discern between large oxygenated molecules from series of oligomers containing repeated small monomers of diverse structures. In the present study, taking advantage from previously established radical vinyl oligomerization of methyl vinylketone (MVK) in the aqueous phase, where relatively simple oligomers containing up to 14 monomers were observed, we have investigated the same reactivity on several other unsaturated water soluble organic compounds (UWSOCs) and on a few mixtures of these precursor compounds. The technique used to characterize the formed oligomers was a traveling wave ion mobility spectrometry coupled to a hybrid quadrupoletime of flight mass spectrometer (IMS-MS) fitted with an electrospray source and ultra-high performance liquid chromatography (UPLC). The technique allows for an additional separation, especially for large ions, containing long carbon chains. We have shown the efficiency of the IMS-mass spectrometry technique to detect oligomers derived from MVK photooxidation in the aqueous phase. The results were then compared to other oligomers, derived from ten other individual biogenic UWSOCs. The technique allowed distinguishing 2 between different oligomers arising from different precursors. It also clearly showed that compounds bearing a non-conjugated unsaturation did not provide oligomerization. Finally, it was shown that the IMS-mass spectrometry technique, applied to mixtures of unsaturated conjugated precursors, exhibited the ability of these precursors to co-oligomerize, i.e. forming only one complex oligomer system bearing monomers of different structures. The results are discussed in terms of atmospheric implications for the detection of oligomers in complex chamber and/or field samples.

show abstract

Aqueous phase oligomerization of methyl vinyl ketone through photooxidation – Part 2: Development of the chemical mechanism and atmospheric implications

Cited by 6 publications

References 73 publications

Rapid Aqueous-Phase Photooxidation of Dimers in the α-Pinene Secondary Organic Aerosol

Rapid Aqueous-Phase Photooxidation of Dimers in the α-Pinene Secondary Organic Aerosol

Cloud Processing of Secondary Organic Aerosol from Isoprene and Methacrolein Photooxidation

Aqueous phase oligomerization of α,β-unsaturated carbonyls and acids investigated using ion mobility spectrometry coupled to mass spectrometry (IMS-MS)

Contact Info

Product

Resources

About