Brown Carbon Production in Ammonium- or Amine-Containing Aerosol Particles by Reactive Uptake of Methylglyoxal and Photolytic Cloud Cycling

Haan, David O. De; Hawkins, L. N.; Welsh, Hannah G.; Pednekar, Raunak; Casar, Jason R.; Pennington, Elyse A.; Loera, Alexia de; Jimenez, Natalie G.; Symons, Michael A.; Zauscher, Melanie; Pajunoja, Aki; Caponi, Lorenzo; Cazaunau, Mathieu; Formenti, Paola; Gratien, Aline; Pangui, Edouard; Doussin, Jean‐François

doi:10.1021/acs.est.7b00159

Cited by 93 publications

(112 citation statements)

References 51 publications

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“…Data availability. The underlying data are publicly available at https://doi.org/10.22371/02.2020.006 (De Haan et al, 2020). Datasets from experiments 1, 2, and 9 are also accessible in the Eurochamp database (Expt 1: https://data.eurochamp.org/data-access/ chamber-experiments/1401b4e7-8a02-481e-8ab0-3ebcfe94fbf2, Doussin, 2020a; Expt 2: https://data.eurochamp.org/data-access/ chamber-experiments/c237d5cd-1fb0-413d-8b86-3643c9a25582, Doussin, 2020b; Expt 9: https://data.eurochamp.org/data-access/ chamber-experiments/75778957-784d-4e6a-84e7-7669f985c0b0, Doussin, 2020c).…”

Section: Discussionmentioning

confidence: 99%

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

et al. 2020

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Abstract. Alpha-dicarbonyl compounds are believed to form brown carbon in the atmosphere via reactions with ammonium sulfate (AS) in cloud droplets and aqueous aerosol particles. In this work, brown carbon formation in AS and other aerosol particles was quantified as a function of relative humidity (RH) during exposure to gas-phase glyoxal (GX) in chamber experiments. Under dry conditions (RH < 5 %), solid AS, AS–glycine, and methylammonium sulfate (MeAS) aerosol particles brown within minutes upon exposure to GX, while sodium sulfate particles do not. When GX concentrations decline, browning goes away, demonstrating that this dry browning process is reversible. Declines in aerosol albedo are found to be a function of [GX]2 and are consistent between AS and AS–glycine aerosol. Dry methylammonium sulfate aerosol browns 4 times more than dry AS aerosol, but deliquesced AS aerosol browns much less than dry AS aerosol. Optical measurements at 405, 450, and 530 nm provide an estimated Ångstrom absorbance coefficient of -16±4. This coefficient and the empirical relationship between GX and albedo are used to estimate an upper limit to global radiative forcing by brown carbon formed by 70 ppt GX reacting with AS (+7.6×10-5 W m−2). This quantity is < 1 % of the total radiative forcing by secondary brown carbon but occurs almost entirely in the ultraviolet range.

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Section: Discussionmentioning

confidence: 99%

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

et al. 2020

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“…S7). Particle acidity could also play a significant role in the gas-to-particle partitioning of aldehydes (Herrmann et al, 2015;Liggio et al, 2005;Gen et al, 2018;De Haan et al, 2018;Kroll et al, 2005), which are precursors for the formation of oxidized organics. However, the higher relative acidity might also be a result of NOC formation.…”

Section: Spams Data Analysismentioning

confidence: 99%

High secondary formation of nitrogen-containing organics (NOCs) and its possible link to oxidized organics and ammonium

Zhang

Lian

et al. 2020

Atmos. Chem. Phys.

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Abstract. Nitrogen-containing organic compounds (NOCs) substantially contribute to light-absorbing organic aerosols, although the atmospheric processes responsible for the secondary formation of these compounds are poorly understood. In this study, seasonal atmospheric processing of NOCs is investigated using single-particle mass spectrometry in urban Guangzhou from 2013 to 2014. The relative abundance of NOCs is found to be strongly enhanced when they are internally mixed with photochemically produced secondary oxidized organics (i.e., formate, acetate, pyruvate, methylglyoxal, glyoxylate, oxalate, malonate, and succinate) and ammonium (NH4+). Moreover, both the hourly detected particle number and the relative abundance of NOCs are highly correlated with those of secondary oxidized organics and NH4+. Therefore, it is hypothesized that the secondary formation of NOCs is most likely linked to oxidized organics and NH4+. Results from both multiple linear regression analysis and positive matrix factorization analysis further show that the relative abundance of NOCs could be well predicted (R2 > 0.7, p < 0.01) by oxidized organics and NH4+. Interestingly, the relative abundance of NOCs is inversely correlated with NH4+, whereas their number fractions are positively correlated. This result suggests that although the formation of NOCs does require the involvement of NH3/NH4+, the relative amount of NH4+ may have a negative effect. Higher humidity and NOx likely facilitates the conversion of oxidized organics to NOCs. Due to the relatively high oxidized organics and NH3/NH4+, the relative contributions of NOCs in summer and fall were higher than those in spring and winter. To the best of our knowledge, this is the first direct field observation study reporting a close association between NOCs and both oxidized organics and NH4+. These findings have substantial implications for the role of NH4+ in the atmosphere, particularly in models that predict the evolution and deposition of NOCs.Highlights. NOCs were highly internally mixed with photochemically produced secondary oxidized organics NOCs could be well predicted by the variations of these oxidized organics and NH4+ Higher relative humidity and NOx may facilitate the conversion of these oxidized organics to NOCs

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“…Most studies have investigated BB BrC aging processes with a focus on aqueous-phase oxidations, such as photochemistry (Chang and Thompson, 2010;Zhao et al, 2015), dark OH-induced oxidation (G. T. Santos and Duarte, 2015), and carbonyl compound reactions with amines/ammonium sulfate (AS) (De Haan et al, 2017;Tang et al, 2016). The oxidation mechanisms and evolution of the optical properties of individual water-soluble organic compounds derived from BB emissions, such as levoglucosan (Holmes and Petrucci, 2006), aromatic acids (P. S. , phenolic compounds (Lavi et al, 2017), nitrophenols (Hems and Abbatt, 2018;Lin et al, 2015), methylglyoxal (De Haan et al, 2017), and some other unsaturated carboxylic acids (Gallimore et al, 2011;Lee and Chan, 2007), have been well illustrated. The results suggest that the chromophoric characteristics of aged BrC are highly variable across different precursors and oxidation conditions.…”

Section: Introductionmentioning

confidence: 99%

The evolutionary behavior of chromophoric brown carbon during ozone aging of fine particles from biomass burning

Fan

Cao

et al. 2020

Atmos. Chem. Phys.

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Abstract. Biomass burning (BB) emits large amounts of brown carbon (BrC); however, the evolutionary behavior of BrC in BB emissions (BB BrC) resulting from complex atmospheric processes is poorly understood. In this study, the transformation of contents and the chromophoric characteristics of BrC in smoke particles emitted by the burning of rice straw (RS), corn straw (CS), and pinewood (PW) under O3 aging are investigated. The O3 aging induced the reduction of light absorption and fluorescence for the BB BrC, suggesting the decomposition of chromophores and fluorophores. These changes were accompanied by a decrease in aromaticity, average molecular weight, and the light absorption capacity for the chromophores, as well as an increase in humification for the fluorophores. The excitation emission matrix combined with a parallel factor analysis revealed that protein-like components (C3) were predominantly decomposed by O3 aging, while the relative distribution of a humic-like component with highly oxygenated chromophores (C4) gradually increased. In general, the humic-like substances (C1 + C2 + C4) were transformed to be the most abundant fluorophores for all the BB BrC samples, which accounted for 84 %–87 % of the total fluorophores in final O3-aged BB BrC. Two-dimensional correlation spectroscopy (2D-COS) was performed on the synchronous fluorescence, which suggested that the RS and CS BrC exhibits the same susceptible fluorophores changes upon O3 aging. It showed that O3 firstly reacted with protein-like fractions (263–289 nm) and then with fulvic-like fractions (333–340 nm). In comparison, the changing sequence of susceptible fluorophores in the PW BrC to O3 was in the order of fulvic-like fluorophores with shorter wavelengths (309 nm), protein-like fluorophores (276 nm), and fulvic-like fluorophores with longer wavelengths (358 nm). The 2D-FTIR-COS (2D-COS combined with FTIR) analysis showed conjugated C=O and aromatic C=C and C=O groups were the most susceptible functional groups to O3 aging for all BB BrC. Moreover, it also revealed a consistent sequential change, which is in the order of aromatic OH; conjugated C=O groups and aromatic C=O; aromatic COO−; and finally lignin-derived C–C, C–H, and C–O groups. Our results provide new insights into the evolutionary behavior of the chromophoric and fluorescent properties of BB BrC during O3 aging, which are of great significance for better understanding the heterogeneous oxidation pathways of BB-derived BrC in the atmospheric environment.

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Brown Carbon Production in Ammonium- or Amine-Containing Aerosol Particles by Reactive Uptake of Methylglyoxal and Photolytic Cloud Cycling

Cited by 93 publications

References 51 publications

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

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

High secondary formation of nitrogen-containing organics (NOCs) and its possible link to oxidized organics and ammonium

The evolutionary behavior of chromophoric brown carbon during ozone aging of fine particles from biomass burning

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