scholarly journals Glyoxal processing by aerosol multiphase chemistry: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

2010 ◽  
Vol 10 (17) ◽  
pp. 8219-8244 ◽  
Author(s):  
B. Ervens ◽  
R. Volkamer
Keyword(s):  
Water Content ◽  
Ammonium Sulfate ◽  
Aqueous Phase ◽  
Liquid Water ◽  
Rate Constants ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Liquid Water Content ◽  
Modeling Framework ◽  
Kinetics Of

Abstract. This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions that form secondary organic aerosol (SOA) in aqueous aerosol particles. Recent laboratory results on glyoxal reactions are reviewed and a consistent set of empirical reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds. Products of these processes include (a) oligomers, (b) nitrogen-containing products, (c) photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry for the same conditions (liquid water content, particle size). The application of the new module including detailed chemical processes in a box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the predicted atmospheric relevance of SOA formation from glyoxal. During day time, a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming ∼5 μg m−3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt). During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids) contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5 < pH < 7). Glyoxal uptake into ammonium sulfate seed under dark conditions can be represented with a single reaction parameter keffupt that does not depend on aerosol loading or water content, which indicates a possibly catalytic role of aerosol water in SOA formation. However, the reversible nature of uptake under dark conditions is not captured by keffupt, and can be parameterized by an effective Henry's law constant including an equilibrium constant Kolig = 1000 (in ammonium sulfate solution). Such reversible glyoxal oligomerization contributes <1% to total predicted SOA masses at any time. Sensitivity tests reveal five parameters that strongly affect the predicted SOA mass from glyoxal: (1) time scales to reach equilibrium states (as opposed to assuming instantaneous equilibrium), (2) particle pH, (3) chemical composition of the bulk aerosol, (4) particle surface composition, and (5) particle liquid water content that is mostly determined by the amount and hygroscopicity of aerosol mass and to a lesser extent by the ambient relative humidity. Glyoxal serves as an example molecule, and the conclusions about SOA formation in aqueous particles can serve for comparative studies of other molecules that form SOA as the result of multiphase chemical processing in aerosol water. This SOA source is currently underrepresented in atmospheric models; if included it is likely to bring SOA predictions (mass and O/C ratio) into better agreement with field observations.

scholarly journals Glyoxal processing outside clouds: towards a kinetic modeling framework of secondary organic aerosol formation in aqueous particles

2010 ◽  
Vol 10 (5) ◽  
pp. 12371-12431 ◽  
Author(s):  
B. Ervens ◽  
R. Volkamer
Keyword(s):  
Aqueous Phase ◽  
Rate Constants ◽  
Surface Composition ◽  
Secondary Organic Aerosol ◽  
Particle Surface ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Aerosol Formation ◽  
Modeling Framework ◽  
Kinetics Of

Abstract. This study presents a modeling framework based on laboratory data to describe the kinetics of glyoxal reactions in aqueous aerosol particles that form secondary organic aerosol (SOA). Recent laboratory results on glyoxal reactions are reviewed and a consistent set of reaction rate constants is derived that captures the kinetics of glyoxal hydration and subsequent reversible and irreversible reactions in aqueous inorganic and water-soluble organic aerosol seeds to form (a) oligomers, (b) nitrogen-containing products, (c) photochemical oxidation products with high molecular weight. These additional aqueous phase processes enhance the SOA formation rate in particles compared to cloud droplets and yield two to three orders of magnitude more SOA than predicted based on reaction schemes for dilute aqueous phase (cloud) chemistry. The application of this new module in a chemical box model demonstrates that both the time scale to reach aqueous phase equilibria and the choice of rate constants of irreversible reactions have a pronounced effect on the atmospheric relevance of SOA formation from glyoxal. During day time a photochemical (most likely radical-initiated) process is the major SOA formation pathway forming ~5 μg m−3 SOA over 12 h (assuming a constant glyoxal mixing ratio of 300 ppt). During night time, reactions of nitrogen-containing compounds (ammonium, amines, amino acids) contribute most to the predicted SOA mass; however, the absolute predicted SOA masses are reduced by an order of magnitude as compared to day time production. The contribution of the ammonium reaction significantly increases in moderately acidic or neutral particles (5<pH<7). Reversible glyoxal oligomerization, parameterized by an equilibrium constant Kolig=1000 (in ammonium sulfate solution), contributes <1% to total predicted SOA masses at any time. Sensitivity tests reveal five parameters that strongly affect the predicted SOA mass from glyoxal: (1) time scales to reach equilibrium states (as opposed to assuming instantaneous equilibrium), (2) particle pH, (3) chemical composition of the bulk aerosol, (4) particle surface composition, and (5) particle liquid water content that is mostly determined by the amount and hygroscopicity of aerosol mass and to a lesser extent by the ambient relative humidity. Glyoxal serves as an example molecule, and the conclusions about SOA formation in aqueous particles can serve for comparative studies also of other molecules that form SOA as the result of multiphase chemical processing in aerosol water. This SOA source is currently underrepresented in atmospheric models; if included it is likely to bring SOA predictions (mass and O/C ratio) into better agreement with field observations.

scholarly journals Using the chemical equilibrium partitioning space to explore factors influencing the phase distribution of compounds involved in secondary organic aerosol formation

2015 ◽  
Vol 15 (6) ◽  
pp. 3395-3412 ◽  
Author(s):  
F. Wania ◽  
Y. D. Lei ◽  
C. Wang ◽  
J. P. D. Abbatt ◽  
K.-U. Goss
Keyword(s):  
Water Content ◽  
Gas Phase ◽  
Aqueous Phase ◽  
Aromatic Hydrocarbons ◽  
Liquid Water ◽  
Phase Distribution ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Liquid Water Content ◽  
The Impact

Abstract. Many atmospheric and chemical variables influence the partitioning equilibrium between gas phase and condensed phases of compounds implicated in the formation of secondary organic aerosol (SOA). The large number of factors and their interaction makes it often difficult to assess their relative importance and concerted impact. Here we introduce a two-dimensional space which maps regions of dominant atmospheric phase distribution within a coordinate system defined by equilibrium partition coefficients between the gas phase, an aqueous phase and a water-insoluble organic matter (WIOM) phase. Placing compounds formed from the oxidation of n-alkanes, terpenes and mono-aromatic hydrocarbons on the maps based on their predicted partitioning properties allows for a simple graphical assessment of their equilibrium phase distribution behaviour. Specifically, it allows for the simultaneous visualisation and quantitative comparison of the impact on phase distribution of changes in atmospheric parameters (such as temperature, salinity, WIOM-phase polarity, organic aerosol load, and liquid water content) and chemical properties (such as oxidation state, molecular size, functionalisation, and dimerisation). The graphical analysis reveals that the addition of hydroxyl, carbonyl and carboxyl groups increases the affinity of aliphatic, alicyclic and aromatic hydrocarbons for the aqueous phase more rapidly than their affinity for WIOM, suggesting that the aqueous phase may often be relevant even for substances that are considerably larger than the C2 and C3 compounds that are typically believed to be associated with aqueous SOA. In particular, the maps identify some compounds that contribute to SOA formation if partitioning to both WIOM and aqueous phase is considered but would remain in the gas phase if either condensed phase were neglected. For example, many semi-volatile α-pinene oxidation products will contribute to aqueous SOA under the conditions of high liquid water content encountered in clouds but would remain vapours in wet aerosol. It is conceivable to develop parameterisations of "partitioning basis sets" that group compounds with comparable partitioning properties, which – when combined with data on the abundance of those groups of compounds – could serve in the simulation of SOA formation.

scholarly journals Using the chemical equilibrium partitioning space to explore factors influencing the phase distribution of compounds involved in secondary organic aerosol formation

2014 ◽  
Vol 14 (19) ◽  
pp. 26545-26590
Author(s):  
F. Wania ◽  
Y. D. Lei ◽  
C. Wang ◽  
J. P. D. Abbatt ◽  
K.-U. Goss
Keyword(s):  
Water Content ◽  
Gas Phase ◽  
Aqueous Phase ◽  
Aromatic Hydrocarbons ◽  
Liquid Water ◽  
Phase Distribution ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Liquid Water Content ◽  
Equilibrium Partitioning

Abstract. Many atmospheric and chemical variables influence the partitioning equilibrium between gas phase and condensed phases of compounds implicated in the formation of secondary organic aerosol (SOA). The large number of factors and their interaction makes it often difficult to assess their relative importance and concerted impact. Here we introduce a two-dimensional space, which maps regions of dominant atmospheric phase distribution within a coordinate system defined by equilibrium partitioning coefficients between the gas phase, an aqueous phase and a water insoluble organic matter (WIOM) phase. Placing compounds formed from the oxidation of n-alkanes, terpenes and mono-aromatic hydrocarbons on the maps based on their predicted partitioning properties allows for a simple graphical assessment of their equilibrium phase distribution behaviour. Specifically, it allows for the simultaneous visualization and quantitative comparison of the impact on phase distribution of changes in atmospheric parameters (such as temperature, salinity, WIOM phase polarity, organic aerosol load, and liquid water content), and chemical properties (such as oxidation state, molecular size, functionalization, and dimerisation). The graphical analysis reveals that the addition of hydroxyl, carbonyl and carboxyl groups increases the affinity of aliphatic, alicyclic and aromatic hydrocarbons for the aqueous phase more rapidly than their affinity for WIOM, suggesting that the aqueous phase may often be relevant even for substances that are considerably larger than the C2 and C3 compounds that are typically believed to be associated with aqueous SOA. In particular, the maps identify some compounds that contribute to SOA formation if partitioning to both WIOM and aqueous phase is considered, but would remain in the gas phase if either condensed phase were neglected. For example, many semi-volatile α-pinene oxidation products will contribute to aqueous SOA under the high liquid water content conditions encountered in clouds, but would remain vapours in wet aerosol. It is conceivable to develop parameterizations of "partitioning basis sets" that group compounds with comparable partitioning properties, which – when combined with data on the abundance of those groups of compounds – could serve in the simulation of SOA formation.

scholarly journals Secondary Organic Aerosol Formation from Acetylene (C<sub>2</sub>H<sub>2</sub>): seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase

2009 ◽  
Vol 9 (6) ◽  
pp. 1907-1928 ◽  
Author(s):  
R. Volkamer ◽  
P. J. Ziemann ◽  
M. J. Molina
Keyword(s):  
Aqueous Phase ◽  
Liquid Water ◽  
Secondary Organic Aerosol ◽  
Cloud Droplet ◽  
Organic Aerosol ◽  
Liquid Water Content ◽  
Water Soluble ◽  
Aerosol Formation ◽  
Cloud Droplets ◽  
Experimental Conditions

Abstract. The lightest Non Methane HydroCarbon (NMHC), i.e., acetylene (C2H2) is found to form secondary organic aerosol (SOA). Contrary to current belief, the number of carbon atoms, n, for a NMHC to act as SOA precursor is lowered to n=2 here. The OH-radical initiated oxidation of C2H2 forms glyoxal (CHOCHO) as the highest yield product, and >99% of the SOA from C2H2 is attributed to CHOCHO. SOA formation from C2H2 and CHOCHO was studied in a photochemical and a dark simulation chamber. Further, the experimental conditions were varied with respect to the chemical composition of the seed aerosols, mild acidification with sulphuric acid (SA, 3<pH<4), and relative humidity (10<RH<90%). The rate of SOA formation is found enhanced by several orders of magnitude in the photochemical system. The SOA yields (YSOA) ranged from 1% to 24% and did not correlate with the organic mass portion of the seed, but increased linearly with liquid water content (LWC) of the seed. For fixed LWC, YSOA varied by more than a factor of five. Water soluble organic carbon (WSOC) photochemistry in the liquid water associated with internally mixed inorganic/WSOC seed aerosols is found responsible for this seed effect. WSOC photochemistry enhances the SOA source from CHOCHO, while seeds containing amino acids (AA) and/or SA showed among the lowest of all YSOA values, and largely suppress the photochemical enhancement on the rate of CHOCHO uptake. Our results give first evidence for the importance of heterogeneous photochemistry of CHOCHO in SOA formation, and identify a potential bias in the currently available YSOA data for other SOA precursor NMHCs. We demonstrate that SOA formation via the aqueous phase is not limited to cloud droplets, but proceeds also in the absence of clouds, i.e., does not stop once a cloud droplet evaporates. Atmospheric models need to be expanded to include SOA formation from WSOC photochemistry of CHOCHO, and possibly other α-dicarbonyls, in aqueous aerosols.

scholarly journals Secondary organic aerosol formation from acetylene (C<sub>2</sub>H<sub>2</sub>): seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase

2008 ◽  
Vol 8 (4) ◽  
pp. 14841-14892 ◽  
Author(s):  
R. Volkamer ◽  
P. J. Ziemann ◽  
M. J. Molina
Keyword(s):  
Aqueous Phase ◽  
Liquid Water ◽  
Secondary Organic Aerosol ◽  
Cloud Droplet ◽  
Organic Aerosol ◽  
Liquid Water Content ◽  
Water Soluble ◽  
Aerosol Formation ◽  
Cloud Droplets ◽  
Experimental Conditions

Abstract. The lightest Non Methane HydroCarbon (NMHC), i.e. acetylene (C2H2) is found to form secondary organic aerosol (SOA). Contrary to current belief, the number of carbon atoms, n, for a NMHC to act as SOA precursor is lowered to n=2 here. The OH-radical initiated oxidation of C2H2 forms glyoxal (CHOCHO) as the highest yield product, and >99% of the SOA from C2H2 is attributed to CHOCHO. SOA formation from C2H2 and CHOCHO was studied in a photochemical and a dark simulation chamber. Further, the experimental conditions were varied with respect to the chemical composition of the seed aerosol, mild acidification with sulphuric acid (SA, 3<pH<4), and relative humidity (10<RH<90%). The rate of SOA formation is found enhanced by several orders of magnitude in the photochemical system. The SOA yields (YSOA) ranged from 1% to 20% and did not correlate with the organic mass portion of the seed, but increased linearly with liquid water content (LWC) of the seed. For fixed LWC, YSOA varied by more than a factor of five. Water soluble organic carbon (WSOC) photochemistry in the liquid water associated with internally mixed inorganic/WSOC seed aerosols is found responsible for this seed effect. WSOC photochemistry enhances the SOA source from CHOCHO, while seeds containing amino acids (AA) and/or SA showed among the lowest of all YSOA values, and largely suppress the photochemical enhancement on the rate of CHOCHO uptake. Our results give first evidence for the importance of heterogeneous photochemistry of CHOCHO in SOA formation, and identify a potential bias in the currently available YSOA data for other SOA precursor NMHCs. We demonstrate that SOA formation via the aqueous phase is not limited to cloud droplets, but proceeds also in the absence of clouds, i.e. does not stop once a cloud droplet evaporates. Atmospheric models need to be expanded to include SOA formation from WSOC photochemistry of CHOCHO, and possibly other α-dicarbonyls, in aqueous aerosols.

scholarly journals Constraining condensed-phase formation kinetics of secondary organic aerosol components from isoprene epoxydiols

2016 ◽  
Vol 16 (3) ◽  
pp. 1245-1254 ◽  
Author(s):  
T. P. Riedel ◽  
Y.-H. Lin ◽  
Z. Zhang ◽  
K. Chu ◽  
J. A. Thornton ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Atmospheric Aerosols ◽  
Rate Constants ◽  
Reaction Rate ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Heterogeneous Reactions ◽  
Model Calculations ◽  
Reaction Rate Constants ◽  
Aerosol Mass

Abstract. Isomeric epoxydiols from isoprene photooxidation (IEPOX) have been shown to produce substantial amounts of secondary organic aerosol (SOA) mass and are therefore considered a major isoprene-derived SOA precursor. Heterogeneous reactions of IEPOX on atmospheric aerosols form various aerosol-phase components or "tracers" that contribute to the SOA mass burden. A limited number of the reaction rate constants for these acid-catalyzed aqueous-phase tracer formation reactions have been constrained through bulk laboratory measurements. We have designed a chemical box model with multiple experimental constraints to explicitly simulate gas- and aqueous-phase reactions during chamber experiments of SOA growth from IEPOX uptake onto acidic sulfate aerosol. The model is constrained by measurements of the IEPOX reactive uptake coefficient, IEPOX and aerosol chamber wall losses, chamber-measured aerosol mass and surface area concentrations, aerosol thermodynamic model calculations, and offline filter-based measurements of SOA tracers. By requiring the model output to match the SOA growth and offline filter measurements collected during the chamber experiments, we derive estimates of the tracer formation reaction rate constants that have not yet been measured or estimated for bulk solutions.

scholarly journals Constraining condensed-phase formation kinetics of secondary organic aerosol components from isoprene epoxydiols

2015 ◽  
Vol 15 (20) ◽  
pp. 28289-28316 ◽  
Author(s):  
T. P. Riedel ◽  
Y.-H. Lin ◽  
Z. Zhang ◽  
K. Chu ◽  
J. A. Thornton ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Atmospheric Aerosols ◽  
Rate Constants ◽  
Reaction Rate ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Heterogeneous Reactions ◽  
Model Calculations ◽  
Reaction Rate Constants ◽  
Aerosol Mass

Abstract. Isomeric epoxydiols from isoprene photooxidation (IEPOX) have been shown to produce substantial amounts of secondary organic aerosol (SOA) mass and are therefore considered a major isoprene-derived SOA precursor. Heterogeneous reactions of IEPOX on atmospheric aerosols form various aerosol-phase components or "tracers" that contribute to the SOA mass burden. A limited number of the reaction rate constants for these acid-catalyzed aqueous-phase tracer formation reactions have been constrained through bulk laboratory measurements. We have designed a chemical box model with multiple experimental constraints to explicitly simulate gas- and aqueous-phase reactions during chamber experiments of SOA growth from IEPOX uptake onto acidic sulfate aerosol. The model is constrained by measurements of the IEPOX reactive uptake coefficient, IEPOX and aerosol chamber wall-losses, chamber-measured aerosol mass and surface area concentrations, aerosol thermodynamic model calculations, and offline filter-based measurements of SOA tracers. By requiring the model output to match the SOA growth and offline filter measurements collected during the chamber experiments, we derive estimates of the tracer formation reaction rate constants that have not yet been measured or estimated for bulk solutions.

Optical Property Measurements and Single Particle Analysis of Secondary Organic Aerosol Produced from the Aqueous-Phase Reaction of Ammonium Sulfate with Methylglyoxal

2018 ◽  
Vol 2 (4) ◽  
pp. 356-365 ◽  
Author(s):  
Deokhyeon Kwon ◽  
Victor W. Or ◽  
Matthew J. Sovers ◽  
Mingjin Tang ◽  
Paul D. Kleiber ◽  
...  
Keyword(s):  
Optical Property ◽  
Ammonium Sulfate ◽  
Aqueous Phase ◽  
Single Particle ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Particle Analysis ◽  
Phase Reaction ◽  
Single Particle Analysis

Kinetics of Limonene Secondary Organic Aerosol Oxidation in the Aqueous Phase

2018 ◽  
Author(s):  
Bartłomiej Witkowski ◽  
Mohammed Al-sharafi ◽  
Tomasz Gierczak
Keyword(s):  
Aqueous Phase ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Kinetics Of

scholarly journals Rapid Aqueous-Phase Photooxidation of Dimers in the α-Pinene Secondary Organic Aerosol

2017 ◽  
Vol 4 (6) ◽  
pp. 205-210 ◽  
Author(s):  
Ran Zhao ◽  
Dana Aljawhary ◽  
Alex K. Y. Lee ◽  
Jonathan P. D. Abbatt
Keyword(s):  
Aqueous Phase ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol
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