Glyoxal's impact on dry ammonium salts:  fast and reversible surface aerosol browning

Haan, David O. De; Hawkins, L. N.; Jansen, Kevin; Welsh, Hannah G.; Pednekar, Raunak; Loera, Alexia de; Jimenez, Natalie G.; Tolbert, Margaret A.; Cazaunau, Mathieu; Gratien, Aline; Bergé, Antonin; Pangui, Edouard; Formenti, Paola; Doussin, Jean‐François

doi:10.5194/acp-2020-203

Cited by 2 publications

(2 citation statements)

References 40 publications

(58 reference statements)

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“…A chamber study of GL uptake to (NH 4 ) 2 SO 4 solution was performed using a high-resolution time-of-flight aerosol mass spectrometer and found that carbon-nitrogen (C-N) compounds are irreversibly produced in the solution (Galloway et al, 2009). However, De Haan et al (2020 have described a rapid but reversible BrC formation in (NH 4 ) 2 SO 4 droplets in dry condition (RH <5 %) using cavity-attenuated phase shift single-scattering albedo spectrometry (De Haan et al, 2020). In addition, Powelson et al (2014) found that the reaction of GL with methylamine is more effective than that with (NH 4 ) 2 SO 4 by using UV-vis and fluorescence spectroscopy (Powelson et al, 2014), while Lian et al (2020) have proven that the synergistic effect of ammonium and amines contributes to the formation of imidazole in cloud processing (Lian et al, 2020).…”

Section: Introductionmentioning

confidence: 99%

Elucidating the critical oligomeric steps in secondary organic aerosol and brown carbon formation

Shi

et al. 2022

Atmos. Chem. Phys.

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Abstract. Small α-dicarbonyls represent the major precursors of secondary organic aerosol (SOA) and brown carbon (BrC) in the atmosphere, but the chemical mechanisms leading to their formation remain unclear. Here we elucidate the fundamental kinetics and mechanisms for aqueous-phase oligomerization of glyoxal (GL) using quantum chemical and kinetic rate calculations. Our results identify several essential isomeric processes for GL, including protonation to yield diol / tetrol and carbenium ions, nucleophilic addition of carbenium ions to diol / tetrol as well as to free methylamine / ammonia (MA / AM), and deprotonation to propagate oligomers and N-heterocycles. Both protonation and nucleophilic addition occur without activation barriers and are dominantly driven by electrostatic attraction. Deprotonation proceeds readily via water molecules in the absence of MA / AM but corresponds to the rate-limiting step for N-containing cationic intermediates to yield N-heterocycles. On the other hand, the latter occurs readily via a catalytic process by acidic anions (e.g., SO42-). A carbenium ion-mediated reaction rate of GL is 4.62 × 10−3 s−1 under atmospheric conditions, in good agreement with the experimental data. Our results provide essential mechanistic and kinetic data for accurate assessment of the role of small α-dicarbonyls in SOA and BrC formation.

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Section: Introductionmentioning

confidence: 99%

Elucidating the critical oligomeric steps in secondary organic aerosol and brown carbon formation

Shi

et al. 2022

Atmos. Chem. Phys.

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“…Therefore, we think that the principal processes observed in our laboratory experiments may also occur in atmospheric glyoxal aerosol particles and, thus, can be used to infer their behavior in the atmosphere, similarly to previous experiments with glyoxal-containing samples and comparable approaches presented in the literature. 23,44,50,52,58,62,63,81 3.2. Time and Temperature Dependence of T g Upon Dilution.…”

Section: Resultsmentioning

confidence: 99%

Glyoxal as a Potential Source of Highly Viscous Aerosol Particles

Peters

Dette

Koop

2021

ACS Earth Space Chem.

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Recent studies have shown that glyoxal may remain in the particle phase of aqueous aerosol particles upon drying despite the high vapor pressure of pure glyoxal, due to the formation of oligomeric glyoxal water adducts with low vapor pressure. Little is known about the phase state of such particles, even though some studies suggested a semisolid or glassy state for dried aqueous glyoxal solutions. In this study, we performed glass transition temperature (T g) measurements on various aqueous glyoxal systems. We show experimentally that very slow and also fast drying of aqueous glyoxal solutions can indeed lead to the formation of highly viscous semisolid and glassy states, both in bulk as well as in aerosolized samples. T g changes with the solute concentration before drying, with drying rate and in the presence of additional solutes such as ammonium sulfate or ammonium bisulfate, even when they are present only in catalytic amounts. Temperature-dependent measurements show that the equilibration between various glyoxal species upon water addition, mimicking atmospheric water uptake upon rising humidity, can range from hours to days. We use the measured glass transition temperatures to infer dependencies of the aqueous phase equilibria between monomer, dimer, and trimer glyoxal species and their water adducts and support these by infrared spectroscopy. Our results imply that aqueous glyoxal aerosols may form highly viscous states at atmospherically relevant conditions.

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Glyoxal's impact on dry ammonium salts: fast and reversible surface aerosol browning

Cited by 2 publications

References 40 publications

Elucidating the critical oligomeric steps in secondary organic aerosol and brown carbon formation

Elucidating the critical oligomeric steps in secondary organic aerosol and brown carbon formation

Glyoxal as a Potential Source of Highly Viscous Aerosol Particles

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