scholarly journals Molecular distributions and isotopic compositions of organic aerosols over the western North Atlantic: Dicarboxylic acids, related compounds, sugars, and secondary organic aerosol tracers

2017 ◽  
Vol 113 ◽  
pp. 229-238 ◽  
Author(s):  
Kimitaka Kawamura ◽  
Mir Md. Mozammal Hoque ◽  
Timothy S. Bates ◽  
Patricia K. Quinn
Keyword(s):  
North Atlantic ◽  
Secondary Organic Aerosol ◽  
Organic Aerosols ◽  
Dicarboxylic Acids ◽  
Organic Aerosol ◽  
Isotopic Compositions ◽  
Related Compounds

scholarly journals Evaluation of Anthropogenic Secondary Organic Aerosol Tracers

2016 ◽  
Author(s):  
Ibrahim M. Al-Naiema ◽  
Elizabeth A. Stone
Keyword(s):  
Phthalic Acid ◽  
Secondary Organic Aerosol ◽  
Dicarboxylic Acids ◽  
Organic Aerosol ◽  
Secondary Source ◽  
Particle Phase ◽  
Water Sensitivity ◽  
Nitrobenzyl Alcohol ◽  
Ambient Concentrations ◽  
Highly Correlated

Abstract. Products of secondary organic aerosol (SOA) from aromatic volatile organic compounds (VOC) – 2,3-dihydroxy-4-oxopentanoic acid, dicarboxylic acids, nitromonoaromatics, and furandiones – were evaluated for their potential to serve as anthropogenic SOA tracers with respect to their 1) ambient concentrations and detectability in PM2.5 in Iowa City, IA, USA, 2) gas-particle partitioning behaviour, and 3) source specificity by way of correlations with primary and secondary source tracers and literature review. A widely used tracer for toluene-derived SOA, 2,3-dihydroxy-4-oxopentanoic acid was only detected in the particle phase (Fp = 1) at low, but consistently measureable ambient concentrations (averaging 0.3 ng m−3). Four aromatic dicarboxylic acids were detected at relatively higher concentrations (9.1–34.5 ng m−3), of which phthalic acid was the most abundant. Phthalic acid had a low particle-phase fraction (Fp = 0.26) likely due to quantitation interferences from phthalic anhydride, while 4-methylphthalic acid was predominantly in the particle phase (Fp = 0.82). Phthalic acid and 4-methyl phthalic acid were both highly correlated with 2,3-dihydroxy-4-oxopentanoic acid (rs = 0.73, p = 0.003; rs = 0.80, p < 0.001, respectively), suggesting that they were derived from aromatic VOC. Isophthalic and terephthalic acids, however, were detected only in the particle phase (Fp = 1) and correlations suggested association with primary emission sources. Nitromonoaromatics were dominated by particle-phase concentrations of 4-nitrocatechol (1.6 ng m−3) and 4-methyl-5-nitrocatechol (1.6 ng m−3) that were associated with biomass burning. Meanwhile, 4-hydroxy-3-nitrobenzyl alcohol was detected in a lower concentration (0.06 ng m−3) in the particle phase only (Fp = 1), and is known as a product of toluene photooxidation. Furandiones in the atmosphere have only been attributed to the photooxidation of aromatic hydrocarbons, however the substantial partitioning toward the gas phase (Fp ≤ 0.16) and their water sensitivity limit their application as tracers. The outcome of this study is the demonstration that 2,3-dihydroxy-4-oxopentanoic acid, phthalic acid, 4-methylphthalic acid, and 4-hydroxy-3-nitrobenzyl alcohol are good candidates for tracing SOA from aromatic VOC.

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 Diurnal variations of organic molecular tracers and stable carbon isotopic compositions in atmospheric aerosols over Mt. Tai in North China Plain: an influence of biomass burning

2012 ◽  
Vol 12 (4) ◽  
pp. 9079-9124
Author(s):  
P. Q. Fu ◽  
K. Kawamura ◽  
J. Chen ◽  
J. Li ◽  
Y. L. Sun ◽  
...  
Keyword(s):  
Organic Carbon ◽  
Biomass Burning ◽  
North China Plain ◽  
North China ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Total Carbon ◽  
Stable Carbon ◽  
Isotopic Compositions ◽  
Carbon Isotopic

Abstract. Organic tracer compounds of tropospheric aerosols, as well as organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and stable carbon isotope ratios (δ13C) of total carbon (TC) have been investigated for aerosol samples collected during early and late periods of Mount Tai eXperiment 2006 (MTX2006) field campaign in North China Plain. Total solvent extracts were investigated by gas chromatography/mass spectrometry. More than 130 organic compounds were detected in the aerosol samples. They were grouped into twelve organic compound classes, including biomass burning tracers, biogenic primary sugars, biogenic secondary organic aerosol (SOA) tracers, and anthropogenic tracers such as phthalates, hopanes and polycyclic aromatic hydrocarbons (PAHs). In early June when the field burning activities of wheat straws in North China Plain were very active, the total identified organics (2090 ± 1170 ng m−3) were double those in late June (926 ± 574 ng m−3). All the compound classes were more abundant in early June than in late June, except phthalate esters, which were higher in late June. Levoglucosan (88–1210 ng m−3, 403 ng m−3) was found as the most abundant single compound in early June, while diisobutyl phthalate was the predominant species in late June. During the biomass-burning period in early June, the diurnal trends of most of the primary and secondary organic aerosol tracers were characterized by the concentration peaks observed at mid-night or in early morning, while in late June most of the organic species peaked in late afternoon. This suggests that smoke plumes from biomass burning can uplift the aerosol particulate matter to a certain altitude and then transported to and encountered the summit of Mt. Tai during nighttime. On the basis of the tracer-based method for the estimation of biomass-burning OC, fungal-spore OC and biogenic secondary organic carbon (SOC), we estimate that an average of 24% (up to 64%) of the OC in the Mt. Tai aerosols was due to biomass burning in early June, followed by the contribution of isoprene SOC (mean 4.3%). In contrast, isoprene SOC was the main contributor (6.6%) to OC, and only 3.0% of the OC was due to biomass burning in late June. In early June, δ13C of TC (−26.6‰ to −23.2‰, mean −25.0‰) were lower than those (−23.9‰ to −21.9‰, mean −22.9‰) in late June. In addition, a strong anti-correlation was found between levoglucosan and δ13C values. This study demonstrates that crop-residue burning activities can significantly enhance the organic aerosol loading and alter the organic molecular compositions and stable carbon isotopic compositions of aerosol particles in the troposphere over North China Plain.

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 Evaluation of anthropogenic secondary organic aerosol tracers from aromatic hydrocarbons

2017 ◽  
Vol 17 (3) ◽  
pp. 2053-2065 ◽  
Author(s):  
Ibrahim M. Al-Naiema ◽  
Elizabeth A. Stone
Keyword(s):  
Aromatic Hydrocarbons ◽  
Phthalic Acid ◽  
Secondary Organic Aerosol ◽  
Dicarboxylic Acids ◽  
Organic Aerosol ◽  
Secondary Source ◽  
Particle Phase ◽  
Water Sensitivity ◽  
Nitrobenzyl Alcohol ◽  
Ambient Concentrations

Abstract. Products of secondary organic aerosol (SOA) from aromatic volatile organic compounds (VOCs) – 2,3-dihydroxy-4-oxopentanoic acid, dicarboxylic acids, nitromonoaromatics, and furandiones – were evaluated for their potential to serve as anthropogenic SOA tracers with respect to their (1) ambient concentrations and detectability in PM2.5 in Iowa City, IA, USA; (2) gas–particle partitioning behaviour; and (3) source specificity by way of correlations with primary and secondary source tracers and literature review. A widely used tracer for toluene-derived SOA, 2,3-dihydroxy-4-oxopentanoic acid was only detected in the particle phase (Fp = 1) at low but consistently measurable ambient concentrations (averaging 0.3 ng m−3). Four aromatic dicarboxylic acids were detected at relatively higher concentrations (9.1–34.5 ng m−3), of which phthalic acid was the most abundant. Phthalic acid had a low particle-phase fraction (Fp =  0.26) likely due to quantitation interferences from phthalic anhydride, while 4-methylphthalic acid was predominantly in the particle phase (Fp = 0.82). Phthalic acid and 4-methylphthalic acid were both highly correlated with 2,3-dihydroxy-4-oxopentanoic acid (rs = 0.73, p = 0.003; rs = 0.80, p < 0.001, respectively), suggesting that they were derived from aromatic VOCs. Isophthalic and terephthalic acids, however, were detected only in the particle phase (Fp = 1), and correlations suggested association with primary emission sources. Nitromonoaromatics were dominated by particle-phase concentrations of 4-nitrocatechol (1.6 ng m−3) and 4-methyl-5-nitrocatechol (1.6 ng m−3) that were associated with biomass burning. Meanwhile, 4-hydroxy-3-nitrobenzyl alcohol was detected in a lower concentration (0.06 ng m−3) in the particle phase only (Fp = 1) and is known as a product of toluene photooxidation. Furandiones in the atmosphere have only been attributed to the photooxidation of aromatic hydrocarbons; however the substantial partitioning toward the gas phase (Fp  ≤  0.16) and their water sensitivity limit their application as tracers. The outcome of this study is the demonstration that 2,3-dihydroxy-4-oxopentanoic acid, phthalic acid, 4-methylphthalic acid, and 4-hydroxy-3-nitrobenzyl alcohol are good candidates for tracing SOA from aromatic VOCs.

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

scholarly journals Secondary organic aerosol production from modern diesel engine emissions

2009 ◽  
Vol 9 (4) ◽  
pp. 17665-17704 ◽  
Author(s):  
S. Samy ◽  
B. Zielinska
Keyword(s):  
Secondary Organic Aerosol ◽  
Dicarboxylic Acids ◽  
Transformation Products ◽  
Organic Aerosol ◽  
Engine Emissions ◽  
No3 Radical ◽  
Group Basis ◽  
Chamber Studies ◽  
The Impact

Abstract. Secondary organic aerosol (SOA) production was observed at significant levels in a series of modern diesel exhaust (DE) aging experiments conducted at the European Outdoor Photoreactor/Simulation Chamber (EUPHORE). The greatest production occurred in DE with toluene addition experiments (>40%), followed by DE with HCHO (for OH radical generation) experiments. A small amount of SOA (3%) was observed for DE in dark with N2O5 (for NO3 radical production) experiments. The analysis for a limited number (54) of polar organic compounds (POC) was conducted to assess the composition of modern DE and the formation of photochemical transformation products. Distinct POC formation in light versus dark experiments suggests the role of OH initiated reactions in these chamber atmospheres. A trend of increasing concentrations of dicarboxylic acids in light versus dark experiments was observed when evaluated on a compound group basis. The four toluene addition experiments in this study were performed at different [tol]o/[NOx]o ratios and displayed an average SOA% yield (in relation to toluene) of 5.3±1.6%, which is compared to past chamber studies that evaluated the impact of [tol]o/[NOx]o on SOA production in more simplified mixtures.

scholarly journals Secondary organic aerosol production from modern diesel engine emissions

2010 ◽  
Vol 10 (2) ◽  
pp. 609-625 ◽  
Author(s):  
S. Samy ◽  
B. Zielinska
Keyword(s):  
Secondary Organic Aerosol ◽  
Dicarboxylic Acids ◽  
Transformation Products ◽  
Organic Aerosol ◽  
Engine Emissions ◽  
No3 Radical ◽  
Group Basis ◽  
Chamber Studies ◽  
The Impact

Abstract. Secondary organic aerosol (SOA) production was observed at significant levels in a series of modern diesel exhaust (DE) aging experiments conducted at the European Outdoor Photoreactor/Simulation Chamber (EUPHORE). The greatest production occurred in DE with toluene addition experiments (>40%), followed by DE with HCHO (for OH radical generation) experiments. A small amount of SOA (3%) was observed for DE in dark with N2O5 (for NO3 radical production) experiments. The analysis for a limited number (54) of polar organic compounds (POC) was conducted to assess the composition of modern DE and the formation of photochemical transformation products. Distinct POC formation in light versus dark experiments suggests the role of OH initiated reactions in these chamber atmospheres. A trend of increasing concentrations of dicarboxylic acids in light versus dark experiments was observed when evaluated on a compound group basis. The four toluene addition experiments in this study were performed at different [tol]o/[NOx]o ratios and displayed an average SOA %yield (in relation to toluene) of 5.3±1.6%, which is compared to past chamber studies that evaluated the impact of [tol]o/[NOx]o on SOA production in more simplified mixtures.

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