scholarly journals Evolution of volatility and composition in sesquiterpene-mixed and <i>α</i>-pinene secondary organic aerosol particles during isothermal evaporation

2021 ◽  
Vol 21 (24) ◽  
pp. 18283-18302
Author(s):  
Zijun Li ◽  
Angela Buchholz ◽  
Arttu Ylisirniö ◽  
Luis Barreira ◽  
Liqing Hao ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Volume Fraction ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Single Type ◽  
Positive Matrix ◽  
Multiple Processes ◽  
Isothermal Evaporation ◽  
Dry Conditions

Abstract. Efforts have been spent on investigating the isothermal evaporation of α-pinene secondary organic aerosol (SOA) particles at ranges of conditions and decoupling the impacts of viscosity and volatility on evaporation. However, little is known about the evaporation behavior of SOA particles from biogenic organic compounds other than α-pinene. In this study, we investigated the isothermal evaporation behavior of the α-pinene and sesquiterpene mixture (SQTmix) SOA particles under a series of relative humidity (RH) conditions. With a set of in situ instruments, we monitored the evolution of particle size, volatility, and composition during evaporation. Our finding demonstrates that the SQTmix SOA particles evaporated slower than the α-pinene ones at any set of RH (expressed with the volume fraction remaining, VFR), which is primarily due to their lower volatility and possibly aided by higher viscosity under dry conditions. We further applied positive matrix factorization (PMF) to the thermal desorption data containing volatility and composition information. Analyzing the net change ratios (NCRs) of each PMF-resolved factor, we can quantitatively compare how each sample factor evolves with increasing evaporation time or RH. When sufficient particulate water content was present in either SOA system, the most volatile sample factor was primarily lost via evaporation, and changes in the other sample factors were mainly governed by aqueous-phase processes. The evolution of each sample factor of the SQTmix SOA particles was controlled by a single type of process, whereas for the α-pinene SOA particles it was regulated by multiple processes. As indicated by the coevolution of VFR and NCR, the effect of aqueous-phase processes could vary from one to another according to particle type, sample factors, and evaporation timescale.

scholarly journals Evolution of volatility and composition in sesquiterpene-mixed and α-pinene secondary organic aerosol particles during isothermal evaporation

2021 ◽  
Author(s):  
Zijun Li ◽  
Angela Buchholz ◽  
Arttu Ylisirniö ◽  
Luis Barreira ◽  
Liqing Hao ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Volume Fraction ◽  
Organic Aerosol ◽  
Single Type ◽  
Positive Matrix ◽  
Evaporation Time ◽  
Multiple Processes ◽  
Isothermal Evaporation ◽  
Dry Conditions

Abstract. Efforts have been spent on investigating the isothermal evaporation of α-pinene SOA particles at ranges of conditions and decoupling the impacts of viscosity and volatility on evaporation. However, little is known about the evaporation behavior of SOA particles from biogenic organic compounds other than α-pinene. In this study, we investigated the isothermal evaporation behaviors of α-pinene (αpin) and sesquiterpene mixture (SQTmix) SOA particles under a series of relative humidity (RH) conditions. With a set of in-situ instruments, we monitored the evolution of particle size, volatility, and composition during evaporation. Our finding demonstrates that the SQTmix SOA particles evaporated slower than the αpin ones at any set of RH (expressed with the volume fraction remaining (VFR)), which is primarily due to their lower volatility and possibly aided by higher viscosity under dry conditions. We further applied positive matrix factorization (PMF) to thermal desorption data containing volatility and composition information. Analyzing the net change ratios (NCRs) of each PMF-resolved factor, we can quantitatively compare how each sample factor evolves with increasing evaporation time/RH. When sufficient particulate water content was present in either SOA system, the most volatile sample factor was primarily lost via evaporation and changes in other sample factors were mainly governed by aqueous-phase processes. The evolution of each sample factor of SQTmix SOA particles was controlled by a single type of process, whereas for αpin SOA particles it was regulated by multiple processes. As indicated by the coevolution of VFR and NCR, the effect of aqueous-phase processes could vary from one to another according to particle type, sample factors and evaporation timescale.

scholarly journals Secondary organic aerosol formation from isoprene photooxidation during cloud condensation–evaporation cycles

2016 ◽  
Vol 16 (3) ◽  
pp. 1747-1760 ◽  
Author(s):  
L. Brégonzio-Rozier ◽  
C. Giorio ◽  
F. Siekmann ◽  
E. Pangui ◽  
S. B. Morales ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Mass Concentration ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Aerosol Formation ◽  
Multiphase Systems ◽  
Dry Conditions ◽  
Water Cloud ◽  
The Impact

Abstract. The impact of cloud events on isoprene secondary organic aerosol (SOA) formation has been studied from an isoprene ∕ NOx ∕ light system in an atmospheric simulation chamber. It was shown that the presence of a liquid water cloud leads to a faster and higher SOA formation than under dry conditions. When a cloud is generated early in the photooxidation reaction, before any SOA formation has occurred, a fast SOA formation is observed with mass yields ranging from 0.002 to 0.004. These yields are 2 and 4 times higher than those observed under dry conditions. When the cloud is generated at a later photooxidation stage, after isoprene SOA is stabilized at its maximum mass concentration, a rapid increase (by a factor of 2 or higher) of the SOA mass concentration is observed. The SOA chemical composition is influenced by cloud generation: the additional SOA formed during cloud events is composed of both organics and nitrate containing species. This SOA formation can be linked to the dissolution of water soluble volatile organic compounds (VOCs) in the aqueous phase and to further aqueous phase reactions. Cloud-induced SOA formation is experimentally demonstrated in this study, thus highlighting the importance of aqueous multiphase systems in atmospheric SOA formation estimations.

scholarly journals Secondary Organic Aerosol formation from isoprene photooxidation during cloud condensation–evaporation cycles

2015 ◽  
Vol 15 (14) ◽  
pp. 20561-20596 ◽  
Author(s):  
L. Brégonzio-Rozier ◽  
C. Giorio ◽  
F. Siekmann ◽  
E. Pangui ◽  
S. B. Morales ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Mass Concentration ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Aerosol Formation ◽  
Multiphase Systems ◽  
Dry Conditions ◽  
Water Cloud ◽  
The Impact

Abstract. The impact of cloud events on isoprene secondary organic aerosol (SOA) formation has been studied from an isoprene/NOx/light system in an atmospheric simulation chamber. It was shown that the presence of a liquid water cloud leads to a faster and higher SOA formation than under dry conditions. When a cloud is generated early in the photooxidation reaction, before any SOA formation has occurred, a fast SOA formation is observed with mass yields ranging from 0.002 to 0.004. These yields are two and four times higher than those observed under dry conditions. When the cloud is generated at a later photooxidation stage, after isoprene SOA is stabilized at its maximum mass concentration, a rapid increase (by a factor of two or higher) of the SOA mass concentration is observed. The SOA chemical composition is influenced by cloud generation: the additional SOA formed during cloud events is composed of both organics and nitrate containing species. This SOA formation can be linked to water soluble volatile organic compounds (VOCs) dissolution in the aqueous phase and to further aqueous phase reactions. Cloud-induced SOA formation is experimentally demonstrated in this study, thus highlighting the importance of aqueous multiphase systems in atmospheric SOA formation estimations.

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

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.

scholarly journals Key parameters controlling OH-initiated formation of secondary organic aerosol in the aqueous phase (aqSOA)

2014 ◽  
Vol 119 (7) ◽  
pp. 3997-4016 ◽  
Author(s):  
Barbara Ervens ◽  
Armin Sorooshian ◽  
Yong B. Lim ◽  
Barbara J. Turpin
Keyword(s):  
Aqueous Phase ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol

The properties and behavior of α-pinene secondary organic aerosol particles exposed to ammonia under dry conditions

2017 ◽  
Vol 19 (9) ◽  
pp. 6497-6507 ◽  
Author(s):  
David M. Bell ◽  
Dan Imre ◽  
Scot T. Martin ◽  
Alla Zelenyuk
Keyword(s):  
Secondary Organic Aerosol ◽  
Chemical Properties ◽  
Particle Morphology ◽  
Organic Aerosol ◽  
Chemical Transformations ◽  
Physical And Chemical Properties ◽  
Dry Conditions ◽  
And Behavior ◽  
Physical And Chemical ◽  
And Chemical Properties

Chemical transformations and aging of secondary organic aerosol (SOA) particles can alter their physical and chemical properties, including particle morphology.

scholarly journals Chemical insights, explicit chemistry, and yields of secondary organic aerosol from OH radical oxidation of methylglyoxal and glyoxal in the aqueous phase

2013 ◽  
Vol 13 (17) ◽  
pp. 8651-8667 ◽  
Author(s):  
Y. B. Lim ◽  
Y. Tan ◽  
B. J. Turpin
Keyword(s):  
Acetic Acid ◽  
Aqueous Phase ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Oxidation Products ◽  
Radical Reactions ◽  
Organic Radical ◽  
Oh Radical ◽  
Radical Oxidation

Abstract. Atmospherically abundant, volatile water-soluble organic compounds formed through gas-phase chemistry (e.g., glyoxal (C2), methylglyoxal (C3), and acetic acid) have great potential to form secondary organic aerosol (SOA) via aqueous chemistry in clouds, fogs, and wet aerosols. This paper (1) provides chemical insights into aqueous-phase OH-radical-initiated reactions leading to SOA formation from methylglyoxal and (2) uses this and a previously published glyoxal mechanism (Lim et al., 2010) to provide SOA yields for use in chemical transport models. Detailed reaction mechanisms including peroxy radical chemistry and a full kinetic model for aqueous photochemistry of acetic acid and methylglyoxal are developed and validated by comparing simulations with the experimental results from previous studies (Tan et al., 2010, 2012). This new methylglyoxal model is then combined with the previous glyoxal model (Lim et al., 2010), and is used to simulate the profiles of products and to estimate SOA yields. At cloud-relevant concentrations (~ 10−6 − ~ 10−3 M; Munger et al., 1995) of glyoxal and methylglyoxal, the major photooxidation products are oxalic acid and pyruvic acid, and simulated SOA yields (by mass) are ~ 120% for glyoxal and ~ 80% for methylglyoxal. During droplet evaporation oligomerization of unreacted methylglyoxal/glyoxal that did not undergo aqueous photooxidation could enhance yields. In wet aerosols, where total dissolved organics are present at much higher concentrations (~ 10 M), the major oxidation products are oligomers formed via organic radical–radical reactions, and simulated SOA yields (by mass) are ~ 90% for both glyoxal and methylglyoxal. Non-radical reactions (e.g., with ammonium) could enhance yields.

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