Single-particle measurements of phase partitioning between primary and secondary organic aerosols

2016 ◽  
Vol 189 ◽  
pp. 31-49 ◽  
Author(s):  
Ellis Shipley Robinson ◽  
Neil M. Donahue ◽  
Adam T. Ahern ◽  
Qing Ye ◽  
Eric Lipsky
Keyword(s):  
Single Particle ◽  
Organic Molecules ◽  
Secondary Organic Aerosols ◽  
Large Fraction ◽  
Organic Aerosols ◽  
Organic Aerosol ◽  
Urban Atmosphere ◽  
Aerosol Formation ◽  
Phase Partitioning ◽  
Single Particle Mass Spectrometry

Organic aerosols provide a measure of complexity in the urban atmosphere. This is because the aerosols start as an external mixture, with many populations from varied local sources, that all interact with each other, with background aerosols, and with condensing vapors from secondary organic aerosol formation. The externally mixed particle populations start to evolve immediately after emission because the organic molecules constituting the particles also form thermodynamic mixtures – solutions – in which a large fraction of the constituents are semi-volatile. The external mixtures are thus well out of thermodynamic equilibrium, with very different activities for many constituents, and yet also have the capacity to relax toward equilibrium via gas-phase exchange of semi-volatile vapors. Here we describe experiments employing quantitative single-particle mass spectrometry designed to explore the extent to which various primary organic aerosol particle populations can interact with each other or with secondary organic aerosols representative of background aerosol populations. These methods allow us to determine when these populations will and when they will not mix with each other, and then to constrain the timescales for that mixing.

scholarly journals Influence of NO<sub>2</sub> on secondary organic aerosol formation from ozonolysis of limonene

2017 ◽  
Author(s):  
Changjin Hu ◽  
Qiao Ma ◽  
Zhi Liu ◽  
Yue Cheng ◽  
Liqing Hao ◽  
...  
Keyword(s):  
Experimental Data ◽  
Secondary Organic Aerosols ◽  
Secondary Organic Aerosol ◽  
Organic Aerosols ◽  
Organic Aerosol ◽  
Chemical Mechanism ◽  
Aerosol Formation ◽  
Model Simulations ◽  
Negative Effect ◽  
Master Chemical Mechanism

Abstract. Limonene has a strong tendency to undergo ozonolysis to form semi-volatile and low-volatility compounds that contribute to secondary organic aerosols (SOAs) both outdoors and indoors. The influence of NO2 on SOA formation from ozonolysis of limonene has been evaluated using chamber experiments and the Master Chemical Mechanism (MCM) coupled with a gas-particle partitioning model in this work. A series of 21 indoor chamber experiments were carried out with or without NO2 under different [O3]0 / [VOC]0 ratios, and these experimental data were compared with the model simulations. Agreement in SOA yields was observed between the experimental observations and model simulations under varying conditions. Generally, SOA mass yields are positively dependent on [O3]0 / [VOC]0 without the presence of NO2. However, the introduction of NO2 leads to a more complicated change in SOA yield, which is shown to be related to initial [O3] / [VOC] ratios. When [O3]0 / [VOC]0 > 2, the introduction of NO2 results in an increase of SOA yield in the range of NO2 studied in this work; whereas a weak negative effect was found for SOA formation according to the introduction of ~ 250 ppbv NO2 under [O3]0 / [VOC]0 

scholarly journals Physico-chemical characterization of secondary organic aerosol derived from catechol and guaiacol as a model substance for atmospheric humic-like substances

2010 ◽  
Vol 10 (7) ◽  
pp. 17369-17405 ◽  
Author(s):  
J. Ofner ◽  
H.-U. Krüger ◽  
H. Grothe ◽  
P. Schmitt-Kopplin ◽  
K. Whitmore ◽  
...  
Keyword(s):  
Functional Groups ◽  
Mass Spectroscopy ◽  
Secondary Organic Aerosols ◽  
Secondary Organic Aerosol ◽  
Organic Aerosols ◽  
Organic Aerosol ◽  
Chemical Diversity ◽  
Spherical Particles ◽  
Aerosol Formation ◽  
Vis Spectroscopy

Abstract. Secondary organic aerosol was produced from the aromatic precursors catechol and guaiacol by reaction with ozone in the presence and absence of simulated sunlight and humidity and investigated for its properties as a proxy for humic-like substances (HULIS). Beside a small particle size, a relatively low molecular weight and typical optical features in the UV/VIS spectral range, HULIS contain a typical aromatic and/or olefinic chemical structure and highly oxidized functional groups within a high chemical diversity. Various methods were used to characterize the secondary organic aerosols obtained: Fourier transform infrared spectroscopy (FTIR) demonstrated the formation of different carbonyl containing functional groups as well as structural and functional differences between aerosols formed at different environmental conditions. UV/VIS spectroscopy of filter samples showed that the particulate matter absorbs far into the visible range up to more than 500 nm. Ultrahigh resolved mass spectroscopy (ICR-FT/MS) determined O/C-ratios between 0.3 and 1 and main molecular weights between 200 and 500 Da. Temperature-programmed-pyrolysis mass spectroscopy identified carboxylic acids and lactones as major functional groups. Particle sizing using CNC-DMPS demonstrated the formation of small particles during a secondary organic aerosol formation process. Particle imaging using field-emission-gun scanning electron microscopy (FEG-SEM) showed spherical particles, forming clusters and chains. Hence, secondary organic aerosols from catechol and guaiacol are appropriate model substances for studies of the processing of aromatic secondary organic aerosols and atmospheric HULIS on the laboratory scale.

scholarly journals Modeling organic aerosols in a megacity: comparison of simple and complex representations of the volatility basis set approach

2010 ◽  
Vol 10 (12) ◽  
pp. 30205-30277 ◽  
Author(s):  
M. Shrivastava ◽  
J. Fast ◽  
R. Easter ◽  
W. I. Gustafson ◽  
R. A. Zaveri ◽  
...  
Keyword(s):  
Gas Phase ◽  
Secondary Organic Aerosol ◽  
Computational Cost ◽  
Organic Aerosols ◽  
Field Measurements ◽  
Organic Aerosol ◽  
Basis Set ◽  
Aerosol Formation ◽  
Secondary Organic Aerosol Formation ◽  
The City

Abstract. The Weather Research and Forecasting model coupled with chemistry (WRF-Chem) is modified to include a volatility basis set (VBS) treatment of secondary organic aerosol formation. The VBS approach, coupled with SAPRC-99 gas-phase chemistry mechanism, is used to model gas-particle partitioning and multiple generations of gas-phase oxidation of organic vapors. In addition to the detailed 9-species VBS, a simplified mechanism using 2 volatility species (2-species VBS) is developed and tested for similarity to the 9-species VBS in terms of both mass and oxygen-to-carbon ratios of organic aerosols in the atmosphere. WRF-Chem results are evaluated against field measurements of organic aerosols collected during the MILAGRO 2006 campaign in the vicinity of Mexico City. The simplified 2-species mechanism reduces the computational cost by a factor of 2 as compared to 9-species VBS. Both ground site and aircraft measurements suggest that the 9-species and 2-species VBS predictions of total organic aerosol mass as well as individual organic aerosol components including primary, secondary, and biomass burning are comparable in magnitude. In addition, oxygen-to-carbon ratio predictions from both approaches agree within 25%, providing evidence that the 2-species VBS is well suited to represent the complex evolution of organic aerosols. Model sensitivity to amount of anthropogenic semi-volatile and intermediate volatility (S/IVOC) precursor emissions is also examined by doubling the default emissions. Both the emission cases significantly under-predict primary organic aerosols in the city center and along aircraft flight transects. Secondary organic aerosols are predicted reasonably well along flight tracks surrounding the city, but are consistently over-predicted downwind of the city. Also, oxygen-to-carbon ratio predictions are significantly improved compared to prior studies by adding 15% oxygen mass per generation of oxidation; however, all modeling cases still under-predict these ratios downwind as compared to measurements, suggesting a need to further improve chemistry parameterizations of secondary organic aerosol formation.

scholarly journals Tracer-based source apportioning of atmospheric organic carbon and the influence of anthropogenic emissions on secondary organic aerosol formation in Hong Kong

2021 ◽  
Vol 21 (13) ◽  
pp. 10589-10608
Author(s):  
Yubo Cheng ◽  
Yiqiu Ma ◽  
Di Hu
Keyword(s):  
Hong Kong ◽  
Organic Carbon ◽  
Secondary Organic Aerosol ◽  
Large Fraction ◽  
Linear Regression Analysis ◽  
Temporal Trends ◽  
Organic Aerosol ◽  
Gas Chromatography Mass Spectrometry ◽  
Multivariate Linear Regression Analysis ◽  
Aerosol Formation

Abstract. Here we conducted comprehensive chemical characterization and source apportionment of 49 PM2.5 samples collected in Hong Kong. Besides the major aerosol constituents, 39 polar organic species, including 14 secondary organic aerosol (SOA) tracers of isoprene, monoterpenes, β-caryophyllene, and naphthalene, were quantified using gas chromatography–mass spectrometry (GC–MS). Six factors, i.e., SOA, secondary sulfate (SS), biomass burning (BB)/SOA, sea salt, marine vessels, and vehicle emissions, were apportioned by positive matrix factorization (PMF) as the major sources of ambient organic carbon (OC) in Hong Kong. The secondary formation, including OC from SOA, SS, and aging of BB plume, was the leading contributor to OC (51.4 %, 2.15 ± 1.37 µg C m−3) throughout the year. We then applied a tracer-based method (TBM) to estimate the SOA formation from the photo-oxidation of four selected precursors, and monoterpene SOA was the most abundant. A Kintecus kinetic model was used to examine the formation channels of isoprene SOA, and the aerosol-phase ring-opening reaction of isoprene epoxydiols (IEPOXs) was found to be the dominant formation pathway. Consistently, IEPOX tracers contributed 94 % to total GC–MS-quantified isoprene SOA tracers. The TBM-estimated secondary organic carbon (SOCTBM) and PMF-apportioned SOC (SOCPMF) showed similar temporal trends; however, SOCTBM only accounted for 26.5 % of SOCPMF, indicating a large fraction of ambient SOA was from other reaction pathways or precursors. Results of Pearson's R and multivariate linear regression analysis showed that NOx processing played a key role in both daytime and nighttime SOA production in the region. Moreover, sulfate had a significant positive linear relationship with SOCPMF and SS-related SOC, and particle acidity was significantly correlated with SOC from the aging of BB.

A Theoretical Perspective of the Structure and Thermodynamics of Secondary Organic Aerosols from Toluene: Molecular Hierarchical Synergistic Effects

2022 ◽  
Author(s):  
Xianli Duan ◽  
Xianyu Song ◽  
Shi Ruifang ◽  
Wang Xuan ◽  
Suhang Chen ◽  
...  
Keyword(s):  
Liquid Fuel ◽  
Secondary Organic Aerosols ◽  
Secondary Organic Aerosol ◽  
Synergistic Effects ◽  
Theoretical Perspective ◽  
Organic Aerosols ◽  
Organic Aerosol ◽  
Underlying Mechanism ◽  
Important Constituent

Toluene is an important constituent of liquid fuel, and it contributes to the formation of secondary organic aerosol (SOA) under photochemical conditions. However, the underlying mechanism of toluene SOA is...

scholarly journals Wintertime secondary organic aerosol formation in Beijing-Tianjin-Hebei (BTH): Contributions of HONO sources and heterogeneous reactions

2018 ◽  
Author(s):  
Li Xing ◽  
Jiarui Wu ◽  
Miriam Elser ◽  
Shengrui Tong ◽  
Suixin Liu ◽  
...  
Keyword(s):  
Organic Aerosols ◽  
Organic Aerosol ◽  
Heterogeneous Reactions ◽  
Weather Research And Forecasting ◽  
Aerosol Formation ◽  
Near Surface ◽  
Formation Pathway ◽  
Residential Living ◽  
The Impact ◽  
Haze Days

Abstract. Organic aerosol (OA) concentrations are simulated over the Beijing-Tianjin-Hebei (BTH) region from 9 to 26 January, 2014 using the Weather Research and Forecasting model coupled with chemistry (WRF-CHEM), with the goal of examining the impact of heterogeneous HONO sources on SOA formation and the SOA formation from different pathways during wintertime haze days. The model generally performs well in simulating air pollutants and organic aerosols against measurements in BTH. Model results show that heterogeneous HONO sources substantially enhance the near-surface SOA formation, increasing regional average near-surface SOA concentration by about 46.3 % during the episode. Oxidation and partitioning of primary organic aerosols treated as semi-volatile dominate the SOA formation, contributing 58.9 % of the near-surface SOA mass in BTH. Irreversible uptake of glyoxal and methylglyoxal on aerosol surfaces constitutes the second most important SOA formation pathway during the episode, with SOA contribution increasing from 8.5 % in non-haze conditions to 30.2 % in haze conditions. Additionally, direct emissions of glyoxal and methylglyoxal from residential living sources contribute about 25.5 % to the total SOA mass on average in BTH. Our study highlights the importance of heterogeneous HONO sources and primary residential emissions of glyoxal and methylglyoxal to SOA formation in winter over BTH.

scholarly journals Modeling organic aerosols in a megacity: comparison of simple and complex representations of the volatility basis set approach

2011 ◽  
Vol 11 (13) ◽  
pp. 6639-6662 ◽  
Author(s):  
M. Shrivastava ◽  
J. Fast ◽  
R. Easter ◽  
W. I. Gustafson ◽  
R. A. Zaveri ◽  
...  
Keyword(s):  
Gas Phase ◽  
Secondary Organic Aerosol ◽  
Computational Cost ◽  
Organic Aerosols ◽  
Field Measurements ◽  
Organic Aerosol ◽  
Basis Set ◽  
Aerosol Formation ◽  
Secondary Organic Aerosol Formation ◽  
The City

Abstract. The Weather Research and Forecasting model coupled with chemistry (WRF-Chem) is modified to include a volatility basis set (VBS) treatment of secondary organic aerosol formation. The VBS approach, coupled with SAPRC-99 gas-phase chemistry mechanism, is used to model gas-particle partitioning and multiple generations of gas-phase oxidation of organic vapors. In addition to the detailed 9-species VBS, a simplified mechanism using 2 volatility species (2-species VBS) is developed and tested for similarity to the 9-species VBS in terms of both mass and oxygen-to-carbon ratios of organic aerosols in the atmosphere. WRF-Chem results are evaluated against field measurements of organic aerosols collected during the MILAGRO 2006 campaign in the vicinity of Mexico City. The simplified 2-species mechanism reduces the computational cost by a factor of 2 as compared to 9-species VBS. Both ground site and aircraft measurements suggest that the 9-species and 2-species VBS predictions of total organic aerosol mass as well as individual organic aerosol components including primary, secondary, and biomass burning are comparable in magnitude. In addition, oxygen-to-carbon ratio predictions from both approaches agree within 25 %, providing evidence that the 2-species VBS is well suited to represent the complex evolution of organic aerosols. Model sensitivity to amount of anthropogenic semi-volatile and intermediate volatility (S/IVOC) precursor emissions is also examined by doubling the default emissions. Both the emission cases significantly under-predict primary organic aerosols in the city center and along aircraft flight transects. Secondary organic aerosols are predicted reasonably well along flight tracks surrounding the city, but are consistently over-predicted downwind of the city. Also, oxygen-to-carbon ratio predictions are significantly improved compared to prior studies by adding 15 % oxygen mass per generation of oxidation; however, all modeling cases still under-predict these ratios downwind as compared to measurements, suggesting a need to further improve chemistry parameterizations of secondary organic aerosol formation.

Effect of hydrophobic primary organic aerosols on secondary organic aerosol formation from ozonolysis ofα-pinene

2007 ◽  
Vol 34 (20) ◽  
Author(s):  
Chen Song ◽  
Rahul A. Zaveri ◽  
M. Lizabeth Alexander ◽  
Joel A. Thornton ◽  
Sasha Madronich ◽  
...  
Keyword(s):  
Secondary Organic Aerosol ◽  
Organic Aerosols ◽  
Organic Aerosol ◽  
Aerosol Formation ◽  
Secondary Organic Aerosol Formation

Organic Aerosol Mixing Observed by Single-Particle Mass Spectrometry

2013 ◽  
Vol 117 (51) ◽  
pp. 13935-13945 ◽  
Author(s):  
Ellis Shipley Robinson ◽  
Rawad Saleh ◽  
Neil M. Donahue
Keyword(s):  
Mass Spectrometry ◽  
Single Particle ◽  
Organic Aerosol ◽  
Particle Mass ◽  
Single Particle Mass Spectrometry
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