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

Abstract

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.

Persistent Uptake of H2O2 onto Ambient PM2.5 via Dark-Fenton Chemistry

“…Here, we selected summer and winter PM 2.5 as representatives for different aerosol compositions to develop parameterization to model the H 2 O 2 loss on urban aerosols. The expression is given in eq based on the results of the curve fitting in Figure b. where Fe s is the dissolved Fe (μg m –3 ), f RH is an empirical formula derived from the observational data to estimate ALWC (μg m –3 ), f RH = 0.0132 × RH 2 – 0.45 × RH + 4.33, RH is relative humidity (%), H 2 O 2 is H 2 O 2 concentration (pptv), and T is temperature (K). More information about parameters can be found in the Supporting Information.…”

“…where Fe s is the dissolved Fe (μg m −3 ), f RH is an empirical formula derived from the observational data to estimate ALWC (μg m −3 ), f RH = 0.0132 × RH 2 − 0.45 × RH + 4.33, 67 RH is relative humidity (%), H 2 O 2 is H 2 O 2 concentration (pptv), and T is temperature (K). More information about parameters can be found in the Supporting Information.…”

Determination of Urban Formaldehyde Emission Ratios in the Shanghai Megacity

“…In addition, the model considered gas–aqueous phase transfer processes based on Schwartz’s kinetic resistance model . However, there exists a significant disparity between the effective field-derived values and theoretical values of the formaldehyde Henry’s constant. , Therefore, the model integrated Mitsuishi et al’s calculated formaldehyde Henry’s constant . For more information on the model setup, see Text S1.…”

Experimental evidence for the elusive ketohydroperoxide pathway and the formation of glyoxal in ethylene ozonolysis

“…The decomposition of ketohydroperoxides in autoxidation chemical systems is a source of OH radicals 19 while glyoxal is the most abundant atmospheric dicarbonyl species and known as a SOA precursor due to its hydrophilic functionality. 20,21 In this experimental work, the veil is lifted on this elusive pathway with the detection of both HPA and glyoxal. A gas mixture made of C 2 H 4 , He, O 2 , and O 3 was adiabatically expanded through a 200 micrometer sized nozzle into the SAPHIRS permanent photoionization end-station 22 at the DESIRS vacuum ultraviolet beamline of synchrotron SOLEIL.…”

“…The decomposition of ketohydroperoxides in autoxidation chemical systems is a source of OH radicals 19 while glyoxal is the most abundant atmospheric dicarbonyl species and known as a SOA precursor due to its hydrophilic functionality. 20,21…”