Hygroscopic growth and CCN activity of secondary organic aerosol produced from dark ozonolysis of γ-terpinene

2022 ◽  
pp. 153010
Author(s):  
Hichem Bouzidi ◽  
Layal Fayad ◽  
Cecile Coeur ◽  
Nicolas Houzel ◽  
Denis Petitprez ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Hygroscopic Growth ◽  
Ccn Activity

Gas-phase kinetics modifies the CCN activity of a biogenic SOA

2018 ◽  
Vol 20 (9) ◽  
pp. 6591-6597
Author(s):  
A. E. Vizenor ◽  
A. A. Asa-Awuku
Keyword(s):  
Particle Size ◽  
Thermodynamic Properties ◽  
Gas Phase ◽  
Secondary Organic Aerosol ◽  
Cloud Condensation Nuclei ◽  
Organic Aerosol ◽  
Aerosol Composition ◽  
Phase Partitioning ◽  
Gas Phase Kinetics ◽  
Ccn Activity

Cloud condensation nuclei (CCN) activity and the hygroscopicity of secondary organic aerosol (SOA) depends on the particle size and composition, explicitly, the thermodynamic properties of the aerosol solute and subsequent interactions with water. The gas-to-aerosol phase partitioning is critical for aerosol composition and thus gas-phase vapors and kinetics can play an important role in the CCN activity of SOA.

scholarly journals Towards closing the gap between hygroscopic growth and activation for secondary organic aerosol – Part 2: Theoretical approaches

2009 ◽  
Vol 9 (12) ◽  
pp. 3999-4009 ◽  
Author(s):  
M. D. Petters ◽  
H. Wex ◽  
C. M. Carrico ◽  
E. Hallbauer ◽  
A. Massling ◽  
...  
Keyword(s):  
Water Activity ◽  
Secondary Organic Aerosol ◽  
Cloud Condensation Nuclei ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Water Mixture ◽  
Hygroscopic Growth ◽  
Ideal Behavior ◽  
Hygroscopic Properties ◽  
Theoretical Approaches

Abstract. We examine the hygroscopic properties of secondary organic aerosol particles generated through the reaction of α-pinene and ozone using a continuous flow reaction chamber. The water activity versus composition relationship is calculated from measurements of growth factors at relative humidities up to 99.6% and from measurements of cloud condensation nuclei activity. The observed relationships are complex, suggesting highly non-ideal behavior for aerosol water contents at relative humidities less than 98%. We present two models that may explain the observed water activity-composition relationship equally well. The first model assumes that the aerosol is a pseudo binary mixture of infinitely water soluble compounds and sparingly soluble compounds that gradually enter the solution as dilution increases. The second model is used to compute the Gibbs free energy of the aerosol-water mixture and shows that the aerosol behaves similarly to what can be expected for single compounds that contain a certain fraction of oxygenated and non-polar functional groups.

scholarly journals Towards closing the gap between hygroscopic growth and activation for secondary organic aerosol – Part 2: Theoretical approaches

2008 ◽  
Vol 8 (6) ◽  
pp. 20839-20867 ◽  
Author(s):  
M. D. Petters ◽  
H. Wex ◽  
C. M. Carrico ◽  
E. Hallbauer ◽  
A. Massling ◽  
...  
Keyword(s):  
Water Activity ◽  
Secondary Organic Aerosol ◽  
Cloud Condensation Nuclei ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Water Mixture ◽  
Hygroscopic Growth ◽  
Ideal Behavior ◽  
Hygroscopic Properties ◽  
Theoretical Approaches

Abstract. We examine the hygroscopic properties of secondary organic aerosol particles generated through the reaction of alpha-pinene and ozone using a continuous flow reaction chamber. The water activity versus composition relationship is calculated from measurements of growth factors at relative humidities up to 99.6% and from measurements of cloud condensation nuclei activity. The observed relationships are complex, suggesting highly non-ideal behavior for aerosol water contents at relative humidities less than 98%. We present two models that may explain the observed water activity-composition relationship equally well. The first model assumes that the aerosol is a pseudo binary mixture of infinitely water soluble compounds and sparingly soluble compounds that gradually enter the solution as dilution increases. The second model is used to compute the Gibbs free energy of the aerosol-water mixture and shows that the aerosol behaves similarly to what can be expected for single compounds that contain a certain fraction of oxygenated and non-polar functional groups.

scholarly journals Relating CCN activity, volatility, and droplet growth kinetics of β-caryophyllene secondary organic aerosol

2009 ◽  
Vol 9 (3) ◽  
pp. 795-812 ◽  
Author(s):  
A. Asa-Awuku ◽  
G. J. Engelhart ◽  
B. H. Lee ◽  
S. N. Pandis ◽  
A. Nenes
Keyword(s):  
Growth Kinetics ◽  
Secondary Organic Aerosol ◽  
Active Material ◽  
Organic Aerosol ◽  
Droplet Formation ◽  
Water Soluble ◽  
Cloud Condensation Nucleus ◽  
Droplet Growth ◽  
Kinetics Of ◽  
Ccn Activity

Abstract. This study investigates the droplet formation characteristics of secondary organic aerosol (SOA) formed during the ozonolysis of sesquiterpene β-caryophyllene (with and without hydroxyl radicals present). Emphasis is placed on understanding the role of semi-volatile material on Cloud Condensation Nucleus (CCN) activity and droplet growth kinetics. Aging of β-caryophyllene SOA significantly affects all CCN-relevant properties measured throughout the experiments. Using a thermodenuder and two CCN instruments, we find that CCN activity is a strong function of temperature (activation diameter at ~0.6% supersaturation: 100±10 nm at 20°C and 130±10 nm at 35°C), suggesting that the hygroscopic fraction of the SOA is volatile. The water-soluble organic carbon (WSOC) is extracted from the SOA and characterized with Köhler Theory Analysis (KTA); the results suggest that the WSOC is composed of low molecular weight (<200 g mol−1) slightly surface-active material that constitute 5–15% of the SOA mass. These properties are similar to the water-soluble fraction of monoterpene SOA, suggesting that predictive understanding of SOA CCN activity requires knowledge of the WSOC fraction but not its exact speciation. Droplet growth kinetics of the CCN are found to be strongly anticorrelated with WSOC fraction, suggesting that the insoluble material in the SOA forms a kinetic barrier that delays droplet growth. Overall, volatilization effects can increase activation diameters by 30%, and depress droplet growth rate by a factor of two; these results may have important implications for the droplet formation characteristics of SOA, and the atmospheric relevance of CCN measurements carried out at temperatures different from ambient.

scholarly journals Laboratory studies of the chemical composition and cloud condensation nuclei (CCN) activity of secondary organic aerosol (SOA) and oxidized primary organic aerosol (OPOA)

2011 ◽  
Vol 11 (17) ◽  
pp. 8913-8928 ◽  
Author(s):  
A. T. Lambe ◽  
T. B. Onasch ◽  
P. Massoli ◽  
D. R. Croasdale ◽  
J. P. Wright ◽  
...  
Keyword(s):  
Flow Reactor ◽  
Secondary Organic Aerosol ◽  
Cloud Condensation Nuclei ◽  
Oxidation Mechanism ◽  
Organic Aerosol ◽  
Anthropogenic Sources ◽  
Oh Radicals ◽  
Condensation Nuclei ◽  
Aerosol Mass ◽  
Ccn Activity

Abstract. Secondary organic aerosol (SOA) and oxidized primary organic aerosol (OPOA) were produced in laboratory experiments from the oxidation of fourteen precursors representing atmospherically relevant biogenic and anthropogenic sources. The SOA and OPOA particles were generated via controlled exposure of precursors to OH radicals and/or O3 in a Potential Aerosol Mass (PAM) flow reactor over timescales equivalent to 1–20 days of atmospheric aging. Aerosol mass spectra of SOA and OPOA were measured with an Aerodyne aerosol mass spectrometer (AMS). The fraction of AMS signal at m/z = 43 and m/z = 44 (f43, f44), the hydrogen-to-carbon (H/C) ratio, and the oxygen-to-carbon (O/C) ratio of the SOA and OPOA were obtained, which are commonly used to characterize the level of oxidation of oxygenated organic aerosol (OOA). The results show that PAM-generated SOA and OPOA can reproduce and extend the observed f44–f43 composition beyond that of ambient OOA as measured by an AMS. Van Krevelen diagrams showing H/C ratio as a function of O/C ratio suggest an oxidation mechanism involving formation of carboxylic acids concurrent with fragmentation of carbon-carbon bonds. Cloud condensation nuclei (CCN) activity of PAM-generated SOA and OPOA was measured as a function of OH exposure and characterized as a function of O/C ratio. CCN activity of the SOA and OPOA, which was characterized in the form of the hygroscopicity parameter κorg, ranged from 8.4×10−4 to 0.28 over measured O/C ratios ranging from 0.05 to 1.42. This range of κorg and O/C ratio is significantly wider than has been previously obtained. To first order, the κorg-to-O/C relationship is well represented by a linear function of the form κorg = (0.18±0.04) ×O/C + 0.03, suggesting that a simple, semi-empirical parameterization of OOA hygroscopicity and oxidation level can be defined for use in chemistry and climate models.

scholarly journals Cloud condensation nuclei (CCN) activity of aliphatic amine secondary aerosol

2014 ◽  
Vol 14 (12) ◽  
pp. 5959-5967 ◽  
Author(s):  
X. Tang ◽  
D. Price ◽  
E. Praske ◽  
D. N. Vu ◽  
K. Purvis-Roberts ◽  
...  
Keyword(s):  
Hydroxyl Radical ◽  
Aliphatic Amine ◽  
Secondary Organic Aerosol ◽  
Cloud Condensation Nuclei ◽  
Organic Aerosol ◽  
Nitrate Radical ◽  
Condensation Nuclei ◽  
Primary Aliphatic Amine ◽  
Secondary Aerosol ◽  
Ccn Activity

Abstract. Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g., hydroxyl radical and nitrate radical). The particle can contain both secondary organic aerosol (SOA) and inorganic salts. The ratio of organic to inorganic materials in the particulate phase influences aerosol hygroscopicity and cloud condensation nuclei (CCN) activity. SOA formed from trimethylamine (TMA) and butylamine (BA) reactions with hydroxyl radical (OH) is composed of organic material of low hygroscopicity (single hygroscopicity parameter, κ, ≤ 0.25). Secondary aerosol formed from the tertiary aliphatic amine (TMA) with N2O5 (source of nitrate radical, NO3) contains less volatile compounds than the primary aliphatic amine (BA) aerosol. As relative humidity (RH) increases, inorganic amine salts are formed as a result of acid–base reactions. The CCN activity of the humid TMA–N2O5 aerosol obeys Zdanovskii, Stokes, and Robinson (ZSR) ideal mixing rules. The humid BA + N2O5 aerosol products were found to be very sensitive to the temperature at which the measurements were made within the streamwise continuous-flow thermal gradient CCN counter; κ ranges from 0.4 to 0.7 dependent on the instrument supersaturation (ss) settings. The variance of the measured aerosol κ values indicates that simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems' κ ranges within 0.2 < κ < 0.7. This work indicates that aerosols formed via nighttime reactions with amines are likely to produce hygroscopic and volatile aerosol, whereas photochemical reactions with OH produce secondary organic aerosol of lower CCN activity. The contributions of semivolatile secondary organic and inorganic material from aliphatic amines must be considered for accurate hygroscopicity and CCN predictions from aliphatic amine systems.

scholarly journals Phase state of secondary organic aerosol in chamber photo-oxidation of mixed precursors

2021 ◽  
Vol 21 (14) ◽  
pp. 11303-11316
Author(s):  
Yu Wang ◽  
Aristeidis Voliotis ◽  
Yunqi Shao ◽  
Taomou Zong ◽  
Xiangxinyue Meng ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Ammonium Sulfate ◽  
Phase State ◽  
Secondary Organic Aerosol ◽  
Inorganic Compounds ◽  
Organic Aerosol ◽  
Phase Behaviour ◽  
Hygroscopic Growth ◽  
Photo Oxidation ◽  
Aerosol Chamber

Abstract. The phase behaviour of aerosol particles plays a profound role in atmospheric physicochemical processes, influencing their physical and optical properties and further impacting climate and air quality. However, understanding of the aerosol phase state is still incomplete, especially that of multicomponent particles which contain inorganic compounds and secondary organic aerosol (SOA) from mixed volatile organic compound (VOC) precursors. We report measurements conducted in the Manchester Aerosol Chamber (MAC) to investigate the aerosol rebounding tendency, measured as the bounce fraction, as a surrogate of the aerosol phase state during SOA formation from photo-oxidation of biogenic (α-pinene and isoprene) and anthropogenic (o-cresol) VOCs and their binary mixtures on deliquescent ammonium sulfate seed. Aerosol phase state is dependent on relative humidity (RH) and chemical composition (key factors determining aerosol water uptake). Liquid (bounce fraction; BF < 0.2) at RH > 80 % and nonliquid behaviour (BF > 0.8) at RH < 30 % were observed, with a liquid-to-nonliquid transition with decreasing RH between 30 % and 80 %. This RH-dependent phase behaviour (RHBF=0.2,0.5,0.8) increased towards a maximum, with an increasing organic–inorganic mass ratio (MRorg/inorg) during SOA formation evolution in all investigated VOC systems. With the use of comparable initial ammonium sulfate seed concentration, the SOA production rate of the VOC systems determines the MRorg/inorg and, consequently, the change in the phase behaviour. Although less important than RH and MRorg/inorg, the SOA composition plays a second-order role, with differences in the liquid-to-nonliquid transition at moderate MRorg/inorg of ∼1 observed between biogenic-only (anthropogenic-free) and anthropogenic-containing VOC systems. Considering the combining role of the RH and chemical composition in aerosol phase state, the BF decreased monotonically with increasing hygroscopic growth factor (GF), and the BF was ∼0 when GF was larger than 1.15. The real atmospheric consequences of our results are that any processes changing ambient RH or MRorg/inorg (aerosol liquid water) will influence their phase state. Where abundant anthropogenic VOCs contribute to SOA, compositional changes in SOA may influence phase behaviour at moderate organic mass fraction (∼50 %) compared with purely biogenic SOA. Further studies are needed on more complex and realistic atmospheric mixtures.

scholarly journals CCN activity and volatility of β-caryophyllene secondary organic aerosol

2012 ◽  
Vol 12 (8) ◽  
pp. 20745-20783
Author(s):  
M. Frosch ◽  
M. Bilde ◽  
A. Nenes ◽  
A. P. Praplan ◽  
Z. Jurányi ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Light Exposure ◽  
Cloud Condensation Nuclei ◽  
Organic Aerosol ◽  
Droplet Growth ◽  
Experimental Conditions ◽  
Initial Injection ◽  
Different Temperatures ◽  
Kinetics Of ◽  
Ccn Activity

Abstract. In a series of smog chamber experiments, the Cloud Condensation Nuclei (CCN) activity of Secondary Organic Aerosol (SOA) generated from ozonolysis of β-caryophyllene was characterized by determining the CCN derived hygroscopicity parameter, κCCN, from experimental data. Two types of CCN counters, operating at different temperatures, were used. The effect of semi-volatile organic compounds on the CCN activity of SOA was studied using a thermodenuder. Overall, SOA was only slightly CCN active (with κCCN in the range 0.001–0.16), and in dark experiments with no OH scavenger present, κCCN decreased when particles were sent through the thermodenuder (with a temperature up to 50 °C). SOA was generated under different experimental conditions: in some experiments, an OH scavenger (2-butanol) was added. SOA from these experiments was less CCN active than SOA produced in experiments without an OH scavenger (i.e. where OH was produced during ozonolysis). In other experiments, lights were turned on, either without or with the addition of HONO (OH source). This led to the formation of more CCN active SOA. SOA was aged up to 30 h through exposure to ozone and (in experiments with no OH scavenger present) to OH. In all experiments, the derived κCCN consistently increased with time after initial injection of β-caryophyllene, showing that chemical ageing increases the CCN activity of β-caryophyllene SOA. κCCN was also observed to depend on supersaturation, which was explained either as an evaporation artifact from semi-volatile SOA (only observed in experiments lacking light exposure) or, alternatively, by effects related to chemical composition depending on dry particle size. Using the method of Threshold Droplet Growth Analysis it was also concluded that the activation kinetics of the SOA do not differ significantly from calibration ammonium sulphate aerosol.

scholarly journals CCN activity and droplet growth kinetics of fresh and aged monoterpene secondary organic aerosol

2008 ◽  
Vol 8 (1) ◽  
pp. 95-135 ◽  
Author(s):  
G. J. Engelhart ◽  
A. Asa-Awuku ◽  
A. Nenes ◽  
S. N. Pandis
Keyword(s):  
Surface Tension ◽  
Growth Kinetics ◽  
Molar Mass ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Water Soluble ◽  
Droplet Growth ◽  
Kohler Theory ◽  
Kinetics Of ◽  
Ccn Activity

Abstract. The ability of secondary organic aerosol (SOA) produced from the ozonolysis of α-pinene and monoterpene mixtures (α-pinene, β-pinene, limonene and 3-carene) to become cloud droplets was investigated. Monoterpene SOA is quite active and would likely be a good source of cloud condensation nuclei (CCN) in the atmosphere. A static CCN counter and a Scanning Mobility CCN Analyser (a Scanning Mobility Particle Sizer coupled with a Continuous Flow counter) were used for the CCN measurements. A decrease in CCN activation diameter for α-pinene SOA of approximately 3 nm h−1 was observed as the aerosol continued to react with oxidants. Hydroxyl radicals further oxidize the SOA particles thereby enhancing the particle CCN activity with time. The initial concentrations of ozone and monoterpene precursor (for concentrations lower than 40 ppb) do not appear to affect the activity of the resulting SOA. Köhler Theory Analysis (KTA) is used to infer the molar mass of the SOA sampled online and offline from atomized filter samples. KTA suggests that the aged aerosol (both from α-pinene and the mixed monoterpene oxidation) is primarily water-soluble (around 70–80%), with an estimated average molar mass of 180±55 g mol−1 (consistent with existing SOA speciation studies). CCN activity measurements of the SOA mixed with (NH4)2SO4 suggest that the organic can depress surface tension by as much as 10 nM m−1 (with respect to pure water). The droplet growth kinetics of SOA samples are similar to (NH4)2SO4, except at low supersaturation, where SOA tends to grow more slowly. The CCN activity of α-pinene and mixed monoterpene SOA can be modelled by a very simple implementation of Köhler theory, assuming complete dissolution of the particles, no dissociation into ions, molecular weight of 180 g mol−1, density of 1.5 g cm−3, and surface tension to within 10–15% of water.

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