Atmospheric Aqueous-Phase Chemistry

Grgić, Irena

doi:10.3390/atmos12010003

Cited by 1 publication

(3 citation statements)

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“…Moreover, those mentioned products include highly oxidized molecules that can remain in the particle phase after complete water evaporation, contributing to the formation of SOA in the atmosphere and enhancing particles' organic mass. 1,5,6 In contrast to gas-phase processing, reactions involved in aqSOA formation have been recognized much later, and their investigation posed a huge challenge to researchers, which could be overcome by strong progress in these studies. 2,7 Many studies focused on aqueous-phase processing of organic compounds such as small carbonyl compounds arising from isoprene oxidation (i.e., glycolaldehyde, 8−10 glyoxal, 11−13 methylglyoxal, 11 methylvinylketone, 14−16 and methacrolein, 16,17 glyoxylic acid, 18,19 pyruvic acid 18,20,21 ) and, more recently, isoprene oxidation products 22−24 or green leaf volatiles.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The atmospheric aqueous phase is now recognized as an important reaction medium for the transformation of organic compounds. , A large amount of liquid water is dispersed in the atmosphere in various forms, i.e., fog, rain, clouds, and deliquescent aerosol, and makes it an important medium where aerosol precursors undergo degradation and consequently form aqueous secondary organic aerosols (aqSOA) . Modeling studies indicate that the global annual production of aqSOA falls within the range of 20–30 Tg .…”

Section: Introductionmentioning

confidence: 99%

“…The increase in the oxygen-to-carbon ratio enhances the hydrophilicity and polarity of the reaction products, making them more susceptible to further processing in aqueous solutions and aqSOA formation while possibly also influencing particle CCN ability. Moreover, those mentioned products include highly oxidized molecules that can remain in the particle phase after complete water evaporation, contributing to the formation of SOA in the atmosphere and enhancing particles’ organic mass. ,, …”

Section: Introductionmentioning

confidence: 99%

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Photo-Oxidation of α-Pinene Oxidation Products in Atmospheric Waters – pH- and Temperature-Dependent Kinetic Studies

Błaziak,

Schaefer,

Rudziński

et al. 2024

J. Phys. Chem. A

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The atmospheric α-pinene oxidation leads to three carboxylic acids: norpinonic acid (NPA), pinic acid (PA), and 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA). In this study, the OH radical kinetics in the aqueous phase of these carboxylic acids were investigated at different temperatures and pH values of solutions. Activation parameters and the corresponding atmospheric lifetimes of the acids in the troposphere were derived. The overall second-order rate constants for the individual speciation forms of the acids (AH and A– for NPA; AH2, AH– and A2– for PA; and AH3, AH2 –, AH2– and A3– for MBTCA) were determined. At 298 K, the rate constants for reactions of protonated forms (AH x ) of NPA, PA, and MBTCA with •OH, were (1.5 ± 0.2) × 109 L mol–1 s–1, (2.4 ± 0.1) × 109 L mol–1 s–1, and (4.1 ± 0.6) × 108 L mol–1 s–1, respectively. For the fully deprotonated forms (A x–) of studied acids, the second-order rate constants were (2.2 ± 0.2) × 109 L mol–1 s–1, (2.8 ± 0.1) × 109 L mol–1 s–1, and (10.2 ± 0.7) × 108 L mol–1 s–1 at 298 K, respectively. It was found that the reactions of NPA and PA with OH radicals are faster than with MBTCA. For MBTCA, the reaction rate depends on pH more strongly at elevated temperatures (>298 K). The atmospheric lifetimes of the acids considered due to their reactivity with •OH were calculated for different model scenarios at a temperature of 283 K and pH = 2 in the aqueous phase. For this purpose, liquid water content (LWC) was used for aerosols and clouds under storm conditions and at various aqueous-phase concentrations of OH radicals. The lifetimes decreased with increasing LWC (from 10–12 m3 m–3 in aerosol to 10–5 m3 m–3 in storms), indicating that the acids undergo significant aqueous processing under realistic atmospheric conditions. Besides, the aerosol systems appeared less effective in removing PA and NPA, with lifetimes ranging from hundreds of days to tens and hundreds of hours, respectively. Clouds were more effective, with lifetimes ranging from tens of hours to a single second or less. MBTCA, which dissolves better in water, was effectively removed in all systems, with the longest lifetime of approximately 90 min.

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