Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

Wyngarden, A. L. Van; Perez-Montaño, Saul; Bui, J. V. H.; Li, E. S. W.; Nelson, T. E.; Ha, Kwonchul; Leong, L.; Iraci, L. T.

doi:10.5194/acp-15-4225-2015

Cited by 13 publications

(20 citation statements)

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“…Li et al: Acrolein reaction with ammonia/ammonium Yu et al, 2011), or Mannich reaction (Nozière and Córdova, 2008;Wang et al, 2010) to form high molecularweight (high-MW) compounds in SOA. For example, compounds that possess two carbonyl groups (dicarbonyls), such as glyoxal and methylglyoxal, are important precursors of aqueous SOA (Galloway et al, 2014;Shapiro et al, 2009;Trainic et al, 2011;Volkamer et al, 2007;Yu et al, 2011;Zhao et al, 2006). A number of laboratory and field studies have highlighted the importance of carbonyl-to-imine reaction for the formation of light-absorbing nitrogen-containing organic compounds (NOCs) from dicarbonyls (De Haan et al, 2011;Hawkins et al, 2018;Lin et al, 2015).…”

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confidence: 99%

“…For example, Powelson et al (2014) investigated the formation of light-absorbing SOA in aqueous reactions of different mono-carbonyl compounds including formaldehyde, acetaldehyde, hydroxyacetone and several dicarbonyl compounds with amines or ammonium salts. Most carbonyl compounds are able to undergo aldol condensation under highly acidic conditions to form oligomers which absorb light in the 300-500 nm range (Nozière and Esteve, 2007;Van Wyngarden et al, 2015). Previous experiments suggest that the light absorptivity of SOA derived from mono-carbonyl compounds is in general smaller than that from reactions of glyoxal and methylglyoxal.…”

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confidence: 99%

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Nitrogen-containing secondary organic aerosol formation by acrolein reaction with ammonia/ammonium

Nizkorodov

Chen

et al. 2019

Atmos. Chem. Phys.

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Abstract. Ammonia-driven carbonyl-to-imine conversion is an important formation pathway to the nitrogen-containing organic compounds (NOCs) in secondary organic aerosols (SOAs). Previous studies have mainly focused on the dicarbonyl compounds as the precursors of light-absorbing NOCs. In this work, we investigated whether acrolein could also act as an NOC precursor. Acrolein is the simplest α, β-unsaturated mono-carbonyl compound, and it is ubiquitous in the atmosphere. Experiments probing multiphase reactions of acrolein as well as bulk aqueous-phase experiments were carried out to study the reactivity of acrolein towards ammonia and ammonium ions. Molecular characterization of the products based on gas chromatography mass spectrometry, high-resolution mass spectrometry, surface-enhanced Raman spectrometry and ultraviolet/visible spectrophotometry was used to propose possible reaction mechanisms. We observed 3-methylpyridine (commonly known as 3-picoline) in the gas phase in Tedlar bags filled with gaseous acrolein and ammonia or ammonium aerosols. In the ammonium-containing aqueous phase, oligomeric compounds with formulas (C3H4O)m(C3H5N)n and pyridinium compounds like (C3H4O)2C6H8N+ were observed as the products. The pathway to 3-methylpyridine was proposed to be the intramolecular carbon–carbon addition of the hemiaminal, which resulted from sequential carbonyl-to-imine conversions of acrolein molecules. The 3-methylpyridine was formed in the aqueous phase, but some of the 3-methylpyridine could revolatilize to the gas phase, explaining the observation of gaseous 3-methylpyridine in the bags. The (C3H4O)2C6H8N+ was a carbonyl-to-hemiaminal product from acrolein dimer and 3-methylpyridine, while the oligomeric products of (C3H4O)m(C3H5N)n were polymers of acroleins and propylene imines formed via carbonyl-to-imine conversion and condensation reactions. The pH value effect on the liquid products was also studied in the bulk aqueous-phase experiments. While the oligomeric compounds were forming in both acidic and alkaline conditions, the pyridinium products favored moderately acidic conditions. Both the oligomeric products and the pyridinium salts are light-absorbing materials. This work suggests that acrolein may serve as a precursor of light-absorbing heterocyclic NOCs in SOA. Therefore, secondary reactions of α, β-unsaturated aldehydes with reduced nitrogen should be taken into account as a source of light-absorbing NOCs in SOA.

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confidence: 99%

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Nitrogen-containing secondary organic aerosol formation by acrolein reaction with ammonia/ammonium

Nizkorodov

Chen

et al. 2019

Atmos. Chem. Phys.

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“…25,26 Studies that deal with formation of organic aerosol in the stratosphere are few, although some infer stratospheric implications from laboratory studies. [27][28][29] Most of the observations of organic aerosol instead have been obtained in the troposphere or in laboratory experiments. 30,31 Primary organic aerosol (POA) and volatile organic compounds (VOC) are oxidized in the atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Formation and composition of the UTLS aerosol

et al. 2019

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Stratospheric aerosol has long been seen as a pure mixture of sulfuric acid and water. Recent measurements, however, found a considerable carbonaceous fraction extending at least 8 km into the stratosphere. This fraction affects the aerosol optical depth (AOD) and the radiative properties, and hence the radiative forcing and climate impact of the stratospheric aerosol. Here we present an investigation based on a decade (2005-2014) of airborne aerosol sampling at 9-12 km altitude in the tropics and the northern hemisphere (NH) aboard the IAGOS-CARIBIC passenger aircraft. We find that the chemical composition of tropospheric aerosol in the tropics differs markedly from that at NH midlatitudes, and, that the carbonaceous stratospheric aerosol is oxygenpoor compared to the tropospheric aerosol. Furthermore, the carbonaceous and sulfurous components of the aerosol in the lowermost stratosphere (LMS) show strong increases in concentration connected with springtime subsidence from overlying stratospheric layers. The LMS concentrations significantly exceed those in the troposphere, thus clearly indicating a stratospheric production of not only the well-established sulfurous aerosol, but also a considerable but less understood carbonaceous component.npj Climate and Atmospheric Science (2019)2:40 ; https://doi.

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“…However, the reference NMR spectrum (SDBS) 68 for the trioxane contains peaks for a triplet at 4.78 ppm, a complex multiplet at 1.67 ppm and a triplet at 0.94 ppm, which were not present in our NMR spectrum ( Figure 5). The absence of the trioxane may be due to the age of this sample (39 days old vs. 7 days old for the FTIR spectrum), since our group recently identified its presence in the NMR spectra of younger films (7 days old) 67 . Preliminary results from our laboratory also indicate the absence of T in the FTIR spectra of older samples in agreement with the results presented in this study.…”

Section: Ethers: Acetals/hemiacetals and Linear/cyclic Polyacetalsmentioning

confidence: 96%

“…Chem. Phys., 2015 67. ) 18a shows the UV-vis spectra of propanal and mixtures of propanal with glyoxal and/or methylglyoxal in 48 wt.…”

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Formation of Organic Films on Sulfuric Acid Solutions at Upper Troposphere and Lower Stratosphere Aerosol Acidities

Perez¹

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The effects of atmospheric aerosols on climate remain uncertain, especially where aerosol chemical composition is not well known. Chemical analysis of aerosols in the upper troposphere (UT) and lower stratosphere (LS) show sulfuric acid (40-80 wt. %) and water as the major components. However, recently, the presence of organic molecules was also reported in UT/LS aerosols which could produce a broad spectrum of chemical reactions that have the potential to alter the aerosol climate properties, so experiments were performed to examine these reactions. Propanal, individually or in mixtures with glyoxal and/or methylglyoxal, combined with sulfuric acid formed highly colored surface films. Since surface films would control aerosol climate properties, the goals of this work are to determine the chemical composition of the films and to determine the effects of aging, organic mixture, and acidity on film composition and formation rates. Films and solutions were analyzed by attenuated total reflectance-FTIR, 1 H NMR and UV-Vis spectroscopies. Results show that aldol condensation products (mainly 2-methyl-2-pentenal and 1,3,5-trimethylbenzene) and acetals (mainly 2,4,6triethyl-1,3,5-trioxane and longer-chain linear polyacetals) are the major species in films formed from propanal. In mixtures of multiple organics, cross-reactions between propanal and glyoxal and/or methylglyoxal were also observed. These results are used to assess the potential for organic films to affect the climate properties of UT/LS aerosols. v 1.

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Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

Cited by 13 publications

References 100 publications

Nitrogen-containing secondary organic aerosol formation by acrolein reaction with ammonia/ammonium

Nitrogen-containing secondary organic aerosol formation by acrolein reaction with ammonia/ammonium

Formation and composition of the UTLS aerosol

Formation of Organic Films on Sulfuric Acid Solutions at Upper Troposphere and Lower Stratosphere Aerosol Acidities

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