Field observational constraints on the controllers in glyoxal (CHOCHO) reactive uptake to aerosol

Kim, Dongwook; Cho, Changmin; Jeong, Seokhan; Lee, Soojin; Nault, Benjamin A.; Campuzano‐Jost, Pedro; Day, Douglas A.; Schroder, Jason C.; Jimenez, José L.; Volkamer, Rainer; Blake, D. R.; Wisthaler, Armin; Fried, Alan; DiGangi, J. P.; Diskin, G. S.; Pusede, S. E.; Hall, Samuel R.; Ullmann, Kirk; Huey, L. G.; Tanner, David J.; Dibb, Jack E.; Knote, Christoph; Min, Kyung‐Eun

doi:10.5194/acp-22-805-2022

Cited by 13 publications

(13 citation statements)

References 120 publications

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“…The calculated γ and k eff,uptake values for different seasons are listed in Table 3. The reactive uptake coefficients of glyoxal were in the range 10 −4 -10 −2 , and the average value of 8.0 × 10 −3 in this study was close to the ones representing the loss of glyoxal by surface uptake during the KORUS-AQ campaign in a very recent study (Kim et al, 2022). The value slightly exceeded the one commonly used in model simulations (γ = 2.9 × 10 −3 ), which was based on an experimental study for (NH 4 ) 2 SO 4 aerosols at 55 % RH (Liggio et al, 2005a), and also far outweighs the uptake coefficients of glyoxal on clean and acidic gas-aged mineral particles (γ = 10 −6 -10 −4 ) (Shen et al, 2016), implying that a real atmospheric aerosol provides a far more reactive interface for physiochemical processes than that of mineral particles.…”

Section: Irreversible Pathways Driven By Hydroxyl Radicalssupporting

confidence: 81%

Reversible and irreversible gas–particle partitioning of dicarbonyl compounds observed in the real atmosphere

Chen

Qin

et al. 2022

Atmos. Chem. Phys.

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Abstract. Glyoxal and methylglyoxal are vital carbonyl compounds in the atmosphere and play substantial roles in radical cycling and ozone formation. The partitioning process of glyoxal and methylglyoxal between the gas and particle phases via reversible and irreversible pathways could efficiently contribute to secondary organic aerosol (SOA) formation. However, the relative importance of two partitioning pathways still remains elusive, especially in the real atmosphere. In this study, we launched five field observations in different seasons and simultaneously measured glyoxal and methylglyoxal in the gas and particle phases. The field-measured gas–particle partitioning coefficients were 5–7 magnitudes higher than the theoretical ones, indicating the significant roles of reversible and irreversible pathways in the partitioning process. The particulate concentration of dicarbonyls and product distribution via the two pathways were further investigated using a box model coupled with the corresponding kinetic mechanisms. We recommended the irreversible reactive uptake coefficient γ for glyoxal and methylglyoxal in different seasons in the real atmosphere, and the average value of 8.0×10-3 for glyoxal and 2.0×10-3 for methylglyoxal best represented the loss of gaseous dicarbonyls by irreversible gas–particle partitioning processes. Compared to the reversible pathways, the irreversible pathways played a dominant role, with a proportion of more than 90 % in the gas–particle partitioning process in the real atmosphere, and the proportion was significantly influenced by relative humidity and inorganic components in aerosols. However, the reversible pathways were also substantial, especially in winter, with a proportion of more than 10 %. The partitioning processes of dicarbonyls in reversible and irreversible pathways jointly contributed to more than 25 % of SOA formation in the real atmosphere. To our knowledge, this study is the first to systemically examine both reversible and irreversible pathways in the ambient atmosphere, strives to narrow the gap between model simulations and field-measured gas–particle partitioning coefficients, and reveals the importance of gas–particle processes for dicarbonyls in SOA formation.

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Section: Irreversible Pathways Driven By Hydroxyl Radicalssupporting

confidence: 81%

Reversible and irreversible gas–particle partitioning of dicarbonyl compounds observed in the real atmosphere

Chen

Qin

et al. 2022

Atmos. Chem. Phys.

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“…Finlayson-Pitts and Pitts, 1986;Volkamer et al, 2001;Fu et al, 2008;Myriokefalitakis et al, 2008;Vrekoussis et al, 2009;Nishino et al, 2010;Li et al, 2016;Chan Miller et al, 2017;Wennberg et al, 2018) and as an important precursor for secondary organic aerosol (SOA) formation and, thus, for the aerosol forcing of climate (e.g. Jang and Kamens, 2001;Liggio et al, 2005b;Volkamer et al, 2007;Lim et al, 2013;Knote et al, 2014;Kim et al, 2022).…”

Section: Introductionmentioning

confidence: 99%

“…Precursor molecules of glyoxal that are mostly (but not exclusively) anthropogenically emitted include alkenes, acetylene, various aromatics, monoterpenes, and other volatile organic compounds (VOCs) with different yields (Volkamer et al, 2001;Fu et al, 2008;Nishino et al, 2010;Taraborrelli et al, 2021). A recent study found that, below 2 km altitude, the production of glyoxal in the city plume of the Seoul metropolitan area (South Korea) was mainly (∼ 59 %) caused by the oxidation of aromatics initiated by hydroxyl radicals (Kim et al, 2022). Glyoxal is also directly emitted in considerable amounts by biomass burning, together with a suite of organic glyoxal precursor molecules in seasonally and regionally amounts with large variations (e.g.…”

Section: Introductionmentioning

confidence: 99%

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Airborne glyoxal measurements in the marine and continental atmosphere: comparison with TROPOMI observations and EMAC simulations

et al. 2023

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Abstract. We report on airborne limb and nadir measurements of vertical profiles and total vertical column densities (VCDs) of glyoxal (C2H2O2) in the troposphere, which were performed aboard the German research aircraft HALO (High Altitude and LOng Range) in different regions and seasons around the globe between 2014 and 2019. The airborne nadir and integrated limb profiles agree excellently among each other. Our airborne observations are further compared to collocated glyoxal measurements of the TROPOspheric Monitoring Instrument (TROPOMI), with good agreement between both data sets for glyoxal observations in (1) pristine terrestrial, (2) pristine marine, (3) mixed polluted, and (4) biomass-burning-affected air masses with high glyoxal concentrations. Exceptions to the overall good agreement are observations of (1) faint and aged biomass burning plumes over the oceans and (2) of low-lying biomass burning or anthropogenic plumes in the terrestrial or marine boundary layer, both of which contain elevated glyoxal that is mostly not captured by TROPOMI. These differences in airborne and satellite-detected glyoxal are most likely caused by the overall small contribution of plumes of a limited extent to the total glyoxal absorption in the atmosphere and the difficulty in remotely detecting weak absorbers located close to low reflective surfaces (e.g. the ocean in the visible wavelength range) or within dense aerosol layers. Observations of glyoxal in aged biomass burning plumes (e.g. observed over the tropical Atlantic off the coast of West Africa in summer 2018, off the coast of Brazil by the end of the dry season 2019, and the East China Sea in spring 2018) could be traced back to related wildfires, such as a plume crossing over the Drake Passage that originated from the Australian bushfires in late 2019. Our observations of glyoxal in such aged biomass burning plumes confirm recent findings of enhanced glyoxal and presumably secondary organic aerosol (SOA) formation in aged wildfire plumes from yet-to-be-identified, longer-lived organic precursor molecules (e.g. aromatics, acetylene, or aliphatic compounds) co-emitted in the fires. Furthermore, elevated glyoxal (median 44 ppt – parts per trillion), as compared to other marine regions (median 10–19 ppt), is observed in the boundary layer over the tropical oceans, which is well in agreement with previous reports. The airborne data sets are further compared to glyoxal simulations performed with the global atmosphere chemistry model EMAC (ECHAM/MESSy Atmospheric Chemistry). When using an EMAC set up that resembles recent EMAC studies focusing on complex chemistry, reasonable agreement is found for pristine air masses (e.g. the unperturbed free and upper troposphere), but a notable glyoxal overestimation of the model exists for regions with high emissions of glyoxal and glyoxal-producing volatile organic compounds (VOCs) from the biosphere (e.g. the Amazon). In all other investigated regions, the model underpredicts glyoxal to varying degrees, in particular when probing mixed emissions from anthropogenic activities (e.g. over continental Europe, the Mediterranean, and East China Sea) and potentially from the sea (e.g. the tropical oceans). Also, the model tends to largely underpredict glyoxal in city plumes and aged biomass burning plumes. The potential causes for these differences are likely to be multifaceted, but they all point to missing glyoxal sources from the degradation of the mixture of potentially longer-chained organic compounds emitted from anthropogenic activities, biomass burning, and from the organic microlayer of the sea surface.

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“…Contrary to the low glyoxal mixing ratios observed in the pristine marine environment, in polluted air glyoxal mixing ratios may reach several 100 ppt (e.g. Lee et al (1998); Volkamer et al (2005aVolkamer et al ( , 2007; Fu et al (2008); Sinreich et al (2010); Baidar et al (2013); Kaiser et al (2015); Volkamer et al (2015); Chan Miller et al (2017); Kluge et al (2020); Kim et al (2022), and others), or even up to 1.6 ppb, as found over a tropical rainforest with large emissions of isoprene in South-East Asia (MacDonald et al, 2012).…”

mentioning

confidence: 96%

Airborne glyoxal measurements in the marine and continental atmosphere: Comparison with TROPOMI observations and EMAC simulations

Kluge

Hüneke

Lerot

et al. 2022

Preprint

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Abstract. We report on airborne Limb and Nadir measurements of vertical profiles and total vertical column densities (VCDs) of glyoxal (C2H2O2) in the troposphere, which were performed from aboard the German research aircraft HALO (High Altitude and Long Range) in different regions and seasons around the globe between 2014 and 2019. The airborne Nadir and integrated Limb profiles excellently agree among each other. Our airborne observations are further compared to collocated glyoxal measurements of the TROPOspheric Monitoring Instrument (TROPOMI), with good agreement between both data sets for glyoxal observations in (1) pristine terrestrial, (2) pristine marine, (3) mixed polluted, and (4) biomass burning affected air masses with high glyoxal concentrations. Exceptions from the overall good agreement are observations of (1) faint and aged biomass burning plumes over the oceans and (2) of low lying biomass burning or anthropogenic plumes in the terrestrial or marine boundary layer, and (3) plumes detected under heavy aerosol loud, both of which contain elevated glyoxal that is mostly not captured by TROPOMI. These differences of airborne and satellite detected glyoxal are most likely caused by the overall small contribution of plumes of limited extent to the total atmospheric absorption by glyoxal and the difficulty to remotely detect weak absorbers located close to low reflective surfaces (e.g. the ocean in the visible wavelength range), or within dense aerosol layers. Observations of glyoxal in aged biomass burning plumes (e.g. observed over the Tropical Atlantic off the coast of West Africa in summer 2018, off the coast of Brazil by the end of the dry season 2019, and the East China Sea in spring 2018) could be traced back to related wildfires, such as a plume crossing over the Drake Passage that originated from the Australian bushfires in late 2019. Our observations of glyoxal in these over days aged biomass burning plumes thus confirm recent findings of enhanced glyoxal and presumably secondary aerosol (SOA) formation in aged wildfire plumes from yet to be identified longer-lived organic precursor molecules (e.g. aromatics, acetylene, or aliphatic compounds) co-emitted in the fires. Further, elevated glyoxal (median 44 ppt) as compared to other marine regions (median 10–19 ppt) is observed in the boundary layer over the tropical oceans, well in agreement with previous reports. The airborne data sets are further compared to glyoxal simulations performed with the global atmosphere-chemistry model EMAC (ECHAM/MESSy Atmospheric Chemistry). When using an EMAC setup that resembles recent EMAC studies focusing on complex chemistry, reasonable agreement is found for pristine air masses (e.g. the unperturbed free and upper troposphere), but notable differences exist for regions with high emissions of glyoxal and glyoxal producing volatile organic compounds (VOC) from the biosphere (e.g. the Amazon), mixed emissions from anthropogenic activities (e.g. continental Europe, the Mediterranean and East China Sea), and potentially from the sea (e.g. the tropical oceans). Also, the model tends to largely under-predict glyoxal in city plumes and aged biomass burning plumes. The potential causes for these differences are likely to be multifaceted, but they all point to missing glyoxal sources from the degradation of the cocktail of (potentially longer-chained) organic compounds emitted from anthropogenic activities, biomass burning, and from the organic micro-layer of the sea.

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Field observational constraints on the controllers in glyoxal (CHOCHO) reactive uptake to aerosol

Cited by 13 publications

References 120 publications

Reversible and irreversible gas–particle partitioning of dicarbonyl compounds observed in the real atmosphere

Reversible and irreversible gas–particle partitioning of dicarbonyl compounds observed in the real atmosphere

Airborne glyoxal measurements in the marine and continental atmosphere: comparison with TROPOMI observations and EMAC simulations

Airborne glyoxal measurements in the marine and continental atmosphere: Comparison with TROPOMI observations and EMAC simulations

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