scholarly journals Impact of Aerosol-Cloud Cycling on Aqueous Secondary Organic Aerosol Formation

2019 ◽  
Author(s):  
William G. Tsui ◽  
Joseph L. Woo ◽  
V. Faye McNeill
Keyword(s):  
Organic Acids ◽  
Aqueous Phase ◽  
Atmospheric Aerosols ◽  
Organic Material ◽  
Time Of Day ◽  
Aerosol Formation ◽  
Cloud Processing ◽  
Aerosol Mass ◽  
Phase Chemistry ◽  
The Impact

Chemical processing of organic material in aqueous atmospheric aerosols and cloudwater is known to form secondary organic aerosols (SOA), although the extent to which each of these processes contributes to total aerosol mass is unclear. In this study, we use GAMMA 5.0, a photochemical box model with coupled gas and aqueous-phase chemistry, to consider the impact of aqueous organic reactions in both aqueous aerosols and clouds on isoprene epoxydiol (IEPOX) SOA over a range of pH for both aqueous phases, including cycling between cloud and aerosol within a single simulation. Low-pH aqueous aerosol, in the absence of organic coatings or other morphology which may limit uptake of IEPOX, is found to be an efficient source of IEPOX SOA, consistent with previous work. Cloudwater at pH 4 or lower is also found to be a potentially significant source of IEPOX SOA. This phenomenon is primarily attributed to the relatively high uptake of IEPOX to clouds as a result of higher water content in clouds as compared to aerosol. For more acidic cloudwater, the aqueous organic material is comprised primarily of IEPOX SOA and lower-volatility organic acids. For both cloudwater and aqueous aerosol, pH is the most significant factor considered in this study in determining the mass of aqueous phase organic acids and IEPOX SOA. Other factors, such as the time of day or sequence of aerosol-to-cloud or cloud-to-aerosol transitions, contribute to less than 15% difference in the final aqSOA fractional composition. The potential significance of cloud processing as a contributor to IEPOX SOA production could account for discrepancies between predicted IEPOX SOA mass from atmospheric models and measured ambient IEPOX SOA mass, or observations of IEPOX SOA in locations where mass transfer limitations are expected in aerosol particles.

scholarly journals Impact of Aerosol-Cloud Cycling on Aqueous Secondary Organic Aerosol Formation

Atmosphere ◽  
2019 ◽  
Vol 10 (11) ◽  
pp. 666 ◽  
Author(s):  
William G. Tsui ◽  
Joseph L. Woo ◽  
V. Faye McNeill
Keyword(s):  
Atmospheric Aerosols ◽  
Organic Material ◽  
Organic Aerosol ◽  
Time Of Day ◽  
Aerosol Formation ◽  
Atmospheric Models ◽  
Cloud Processing ◽  
Aerosol Mass ◽  
Phase Chemistry ◽  
The Impact

Chemical processing of organic material in aqueous atmospheric aerosols and cloudwater is known to form secondary organic aerosols (SOA), although the extent to which each of these processes contributes to total aerosol mass is unclear. In this study, we use GAMMA 5.0, a photochemical box model with coupled gas and aqueous-phase chemistry, to consider the impact of aqueous organic reactions in both aqueous aerosols and clouds on isoprene epoxydiol (IEPOX) SOA over a range of pH for both aqueous phases, including cycling between cloud and aerosol within a single simulation. Low pH aqueous aerosol, in the absence of organic coatings or other morphology which may limit uptake of IEPOX, is found to be an efficient source of IEPOX SOA, consistent with previous work. Cloudwater at pH 4 or lower is also found to be a potentially significant source of IEPOX SOA. This phenomenon is primarily attributed to the relatively high uptake of IEPOX to clouds as a result of higher water content in clouds as compared with aerosol. For more acidic cloudwater, the aqueous organic material is comprised primarily of IEPOX SOA and lower-volatility organic acids. Both cloudwater pH and the time of day or sequence of aerosol-to-cloud or cloud-to-aerosol transitions impacted final aqueous SOA mass and composition in the simulations. The potential significance of cloud processing as a contributor to IEPOX SOA production could account for discrepancies between predicted IEPOX SOA mass from atmospheric models and measured ambient IEPOX SOA mass, or observations of IEPOX SOA in locations where mass transfer limitations are expected in aerosol particles.

scholarly journals Seasonal differences in formation processes of oxidized organic aerosol near Houston, TX

2018 ◽  
Author(s):  
Qili Dai ◽  
Benjamin C. Schulze ◽  
Xiaohui Bi ◽  
Alexander A. T. Bui ◽  
Fangzhou Guo ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Organic Aerosol ◽  
Liquid Water Content ◽  
Ratio Method ◽  
Organic Nitrate ◽  
Aerosol Formation ◽  
Light Rain ◽  
Aerosol Mass ◽  
Secondary Aerosols ◽  
Phase Chemistry

Abstract. Submicron aerosol was measured to the southwest of Houston, Texas during winter and summer 2014 to investigate its seasonal variability. Data from a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) indicated that organic aerosol (OA) was the largest component of non-refractory submicron particulate matter (NR-PM1) (on average, 46 ± 13 % and 55 ± 18 % of the NR-PM1 mass loading in winter and summer, respectively). Positive matrix factorization (PMF) analysis of the OA mass spectra demonstrated that two classes of oxygenated OA (less and more-oxidized OOA, LO and MO) together dominated OA mass in summer (77 %) and accounted for 42 % of OA mass in winter. The fraction of LO-OOA (out of total OOA) is higher in summer (69 %) than in winter (44 %). Secondary aerosols (sulfate + nitrate + ammonium + OOA) accounted for ~ 76 % and 89 % of NR-PM1 mass in winter and summer, respectively, indicating NR-PM1 mass was driven mostly by secondary aerosol formation regardless of the season. The mass loadings and diurnal patterns of these secondary aerosols show a clear winter/summer contrast. Organic nitrate (ON) concentrations were estimated using the NOx+ ratio method, with an average contribution of ~ 15 % and 37 % to OA during winter and summer campaign, respectively. The estimated ON in summer strongly correlated with LO-OOA (r = 0.73) and was enhanced at nighttime. The relative importance of aqueous-phase chemistry and photochemistry in processing OOA was investigated by examining the relationship of aerosol liquid water content (LWC) and the sum of ozone (O3) and nitrogen dioxide (NO2) (Ox = O3 + NO2) with LO-OOA and MO-OOA. The processing mechanism of LO-OOA apparently depended on relative humidity (RH). In periods of RH  80 %, these effects were opposite that of low RH periods. Both photochemistry and aqueous-phase processing appear to facilitate MO-OOA formation except during periods of high LWC, which is likely a result of wet removal during periods of light rain. The nighttime increases of MO-OOA during winter and summer were 0.013 and 0.01 μg MO-OOA per μg of LWC, respectively. The increase of LO-OOA was larger than that for MO-OOA, with increase rates of 0.033 and 0.055 μg LO-OOA per μg of LWC at night during winter and summer, respectively. On average, the mass concentration of LO-OOA in summer was elevated by nearly 1.2 μg m−3 for a ~ 20 μg change in LWC, which is accompanied by a 40 ppb change in Ox.

The Impact of the Aqueous Phase Chemistry of HNO4 on Gas Phase Tropospheric Chemistry

2001 ◽  
Vol 32 ◽  
pp. 269-270
Author(s):  
J.E. WILLIAMS ◽  
F.J. DENTENER ◽  
A.R. van den BERG
Keyword(s):  
Gas Phase ◽  
Aqueous Phase ◽  
Tropospheric Chemistry ◽  
Phase Chemistry ◽  
The Impact

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 The real part of the refractive indices and effective densities for chemically segregated ambient aerosols in Guangzhou measured by a single-particle aerosol mass spectrometer

2016 ◽  
Vol 16 (4) ◽  
pp. 2631-2640 ◽  
Author(s):  
Guohua Zhang ◽  
Xinhui Bi ◽  
Ning Qiu ◽  
Bingxue Han ◽  
Qinhao Lin ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Atmospheric Aerosols ◽  
Single Particle ◽  
Refractive Indices ◽  
Chemical Compositions ◽  
Aerosol Mass Spectrometer ◽  
The Real ◽  
Aerosol Mass ◽  
Wide Range ◽  
The Impact

Abstract. Knowledge on the microphysical properties of atmospheric aerosols is essential to better evaluate their radiative forcing. This paper presents an estimate of the real part of the refractive indices (n) and effective densities (ρeff) of chemically segregated atmospheric aerosols in Guangzhou, China. Vacuum aerodynamic diameter, chemical compositions, and light-scattering intensities of individual particles were simultaneously measured by a single-particle aerosol mass spectrometer (SPAMS) during the fall of 2012. On the basis of Mie theory, n at a wavelength of 532 nm and ρeff were estimated for 17 particle types in four categories: organics (OC), elemental carbon (EC), internally mixed EC and OC (ECOC), and Metal-rich. The results indicate the presence of spherical or nearly spherical shapes for the majority of particle types, whose partial scattering cross-section versus sizes were well fitted to Mie theoretical modeling results. While sharing n in a narrow range (1.47–1.53), majority of particle types exhibited a wide range of ρeff (0.87–1.51 g cm−3). The OC group is associated with the lowest ρeff (0.87–1.07 g cm−3), and the Metal-rich group with the highest ones (1.29–1.51 g cm−3). It is noteworthy that a specific EC type exhibits a complex scattering curve versus size due to the presence of both compact and irregularly shaped particles. Overall, the results on the detailed relationship between physical and chemical properties benefits future research on the impact of aerosols on visibility and climate.

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 Characterisation of solvent extractable organic constituents in atmospheric particulate matter: an overview

2008 ◽  
Vol 80 (1) ◽  
pp. 21-82 ◽  
Author(s):  
Célia A. Alves
Keyword(s):  
Particulate Matter ◽  
Organic Compounds ◽  
Atmospheric Aerosols ◽  
Current Knowledge ◽  
Atmospheric Particulate Matter ◽  
Aerosol Formation ◽  
Atmospheric Particulate ◽  
Organic Constituents ◽  
Geochemical Parameters ◽  
The Impact

In spite of accounting for 10-70% of the atmospheric aerosol mass, particulate-phase organic compounds are not well characterised, and many aspects of aerosol formation and evolution are still unknown. The growing awareness of the impact of particulate aerosols on climate, and the incompletely recognised but serious effects of anthropogenic constituents on air quality and human health, have conducted to several scientific studies. These investigations have provided information about the behaviour of atmospheric particulate matter and the description of the character of its carbonaceous content. The compilation of such results is important as they append to the emergent global-wide dataset of the organic composition of atmospheric aerosols. The contribution of the major emission sources to regional particulate pollution can be diagnosed by using specific molecular markers. This overview is mainly focused on results obtained with gas chromatography coupled with mass spectrometry, since it is the analytical method of choice in elucidating the solvent-extractable organic compounds in atmospheric particulate matter. A synopsis of the selection of organic tracers and the application of geochemical parameters to the analysis of organic constituents as a tool for source apportionment is shown here. Besides the assessment of current knowledge, this paper also presents the identification of further areas of concern.

scholarly journals Characterization of aerosol and cloud water at a mountain site during WACS 2010: secondary organic aerosol formation through oxidative cloud processing

2012 ◽  
Vol 12 (2) ◽  
pp. 6019-6047 ◽  
Author(s):  
A. K. Y. Lee ◽  
K. L. Hayden ◽  
P. Herckes ◽  
W. R. Leaitch ◽  
J. Liggio ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Cloud Water ◽  
Water Soluble ◽  
Photochemical Oxidation ◽  
Aerosol Formation ◽  
Aerosol Mass ◽  
Dissolved Organics ◽  
Organic Spectra

Abstract. The water-soluble fractions of aerosol samples and cloud water collected during Whistler Aerosol and Cloud Study (WACS 2010) were analyzed using an Aerodyne aerosol mass spectrometer (AMS). This is the first study to report AMS organic spectra of re-aerosolized cloud water, and to make direct comparison between the AMS spectra of cloud water and aerosol samples collected at the same location. In general, the aerosol and cloud organic spectra were very similar, indicating that the cloud water organics likely originated from secondary organic aerosol (SOA) formed nearby. By using a photochemical reactor to oxidize both aerosol filter extracts and cloud water, we find evidence that fragmentation of aerosol water-soluble organics increases their volatility during oxidation. By contrast, enhancement of AMS-measurable organic mass by up to 30% was observed during aqueous-phase photochemical oxidation of cloud water organics. We propose that additional SOA material was produced by functionalizing dissolved organics via OH oxidation, where these dissolved organics are sufficiently volatile that they are not usually part of the aerosol. This work points out that water-soluble organic compounds of intermediate volatility (IVOC), such as cis-pinonic acid, produced via gas-phase oxidation of monoterpenes, can be important aqueous-phase SOA precursors in a biogenic-rich environment.

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