scholarly journals Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

2011 ◽  
Vol 3 (2) ◽  
pp. 133-139 ◽  
Author(s):  
Jesse H. Kroll ◽  
Neil M. Donahue ◽  
Jose L. Jimenez ◽  
Sean H. Kessler ◽  
Manjula R. Canagaratna ◽  
...  
Keyword(s):  
Oxidation State ◽  
Organic Aerosol ◽  
Carbon Oxidation

scholarly journals Aircraft observations of the chemical composition and aging of aerosol in the Manaus urban plume during GoAmazon 2014/5

2018 ◽  
Vol 18 (14) ◽  
pp. 10773-10797 ◽  
Author(s):  
John E. Shilling ◽  
Mikhail S. Pekour ◽  
Edward C. Fortner ◽  
Paulo Artaxo ◽  
Suzane de Sá ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Oxidation State ◽  
Biomass Burning ◽  
Urban Pollution ◽  
Organic Aerosol ◽  
Dry Season ◽  
Carbon Oxidation ◽  
Wet Season ◽  
The Mean ◽  
American Cities

Abstract. The Green Ocean Amazon (GoAmazon 2014/5) campaign, conducted from January 2014 to December 2015 in the vicinity of Manaus, Brazil, was designed to study the aerosol life cycle and aerosol–cloud interactions in both pristine and anthropogenically influenced conditions. As part of this campaign, the U.S. Department of Energy (DOE) Gulfstream 1 (G-1) research aircraft was deployed from 17 February to 25 March 2014 (wet season) and 6 September to 5 October 2014 (dry season) to investigate aerosol and cloud properties aloft. Here, we present results from the G-1 deployments focusing on measurements of the aerosol chemical composition and secondary organic aerosol (SOA) formation and aging. In the first portion of the paper, we provide an overview of the data and compare and contrast the data from the wet and dry season. Organic aerosol (OA) dominates the deployment-averaged chemical composition, comprising 80 % of the non-refractory PM1 aerosol mass, with sulfate comprising 14 %, nitrate 2 %, and ammonium 4 %. This product distribution was unchanged between seasons, despite the fact that total aerosol loading was significantly higher in the dry season and that regional and local biomass burning was a significant source of OA mass in the dry, but not wet, season. However, the OA was more oxidized in the dry season, with the median of the mean carbon oxidation state increasing from −0.45 in the wet season to −0.02 in the dry season. In the second portion of the paper, we discuss the evolution of the Manaus plume, focusing on 13 March 2014, one of the exemplary days in the wet season. On this flight, we observe a clear increase in OA concentrations in the Manaus plume relative to the background. As the plume is transported downwind and ages, we observe dynamic changes in the OA. The mean carbon oxidation state of the OA increases from −0.6 to −0.45 during the 4–5 h of photochemical aging. Hydrocarbon-like organic aerosol (HOA) mass is lost, with ΔHOA∕ΔCO values decreasing from 17.6 µg m−3 ppmv−1 over Manaus to 10.6 µg m−3 ppmv−1 95 km downwind. Loss of HOA is balanced out by formation of oxygenated organic aerosol (OOA), with ΔOOA∕ΔCO increasing from 9.2 to 23.1 µg m−3 ppmv−1. Because hydrocarbon-like organic aerosol (HOA) loss is balanced by OOA formation, we observe little change in the net Δorg∕ΔCO values; Δorg∕ΔCO averages 31 µg m−3 ppmv−1 and does not increase with aging. Analysis of the Manaus plume evolution using data from two additional flights in the wet season showed similar trends in Δorg∕ΔCO to the 13 March flight; Δorg∕ΔCO values averaged 34 µg m−3 ppmv−1 and showed little change over 4–6.5 h of aging. Our observation of constant Δorg∕ΔCO are in contrast to literature studies of the outflow of several North American cities, which report significant increases in Δorg∕ΔCO for the first day of plume aging. These observations suggest that SOA formation in the Manaus plume occurs, at least in part, by a different mechanism than observed in urban outflow plumes in most other literature studies. Constant Δorg∕ΔCO with plume aging has been observed in many biomass burning plumes, but we are unaware of reports of fresh urban emissions aging in this manner. These observations show that urban pollution emitted from Manaus in the wet season forms less particulate downwind as it ages than urban pollution emitted from North American cities.

scholarly journals Enhancement of Secondary Organic Aerosol Formation and its Oxidation State by SO<sub>2</sub> during Photooxidation of 2-Methoxyphenol

2018 ◽  
Author(s):  
Changgeng Liu ◽  
Tianzeng Chen ◽  
Yongchun Liu ◽  
Jun Liu ◽  
Hong He ◽  
...  
Keyword(s):  
Oxidation State ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Wood Smoke ◽  
Organic Nitrates ◽  
Carbon Oxidation ◽  
Formation Processes ◽  
Aerosol Formation ◽  
Product Model ◽  
Seed Particles

Abstract. 2-Methoxyphenol (guaiacol) is derived from the lignin pyrolysis and taken as a potential tracer for wood smoke emissions. In this work, the effect of SO2 at atmospheric levels (0–56 ppb) on secondary organic aerosol (SOA) formation and its oxidation state during guaiacol photooxidation was investigated in the presence of various inorganic seed particles (NaCl and (NH4)2SO4). Without SO2 and seed particles, SOA yields (9.46–26.37 %) obtained at different guaiacol concentration (138.83–2197.36 μg m−3) could be well expressed by a one-product model. The presence of SO2 resulted in enhancing SOA yield by 14.05–23.66 %. With (NH4)2SO4 and NaCl seed particles, SOA yield was enhanced by 23.06 % and 29.57 %, respectively, which further increased significantly to 29.78–53.47 % in the presence of SO2, suggesting that SO2 and seed particles have a synergetic contribution to SOA formation. It should be noted that SO2 was found to be in favor of increasing the carbon oxidation state (OSC) of SOA, indicating that the functionalization reaction should be more dominant than oligomerization reaction. In addition, the average N/C ratio of SOA was 0.037, which revealed that NOx participated in the photooxidation process, consequently leading to the formation of organic nitrates. The experimental results demonstrate the importance of SO2 on the formation processes of SOA and organosulfates, and also are helpful to further understand SOA formation from the atmospheric photooxidation of guaiacol and its subsequent impacts on air quality and climate.

scholarly journals Aging of secondary organic aerosol from small aromatic VOCs: changes in chemical composition, mass yield, volatility and hygroscopicity

2014 ◽  
Vol 14 (22) ◽  
pp. 31441-31481 ◽  
Author(s):  
L. Hildebrandt Ruiz ◽  
A. L. Paciga ◽  
K. Cerully ◽  
A. Nenes ◽  
N. M. Donahue ◽  
...  
Keyword(s):  
Oxidation State ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Clear Correlation ◽  
Carbon Oxidation ◽  
Mass Yield ◽  
Initial Formation ◽  
Chemical Aging ◽  
Photo Oxidation ◽  
Volatile Organic

Abstract. Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form and transform SOA from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx. The effects of chemical aging on organic aerosol (OA) composition, mass yield, volatility and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state OSC) and mass yield. The OA oxidation state generally increased during photo-oxidation, and the final OA OS C ranged from −0.29 to 0.45 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.

scholarly journals Enhancement of secondary organic aerosol formation and its oxidation state by SO<sub>2</sub> during photooxidation of 2-methoxyphenol

2019 ◽  
Vol 19 (4) ◽  
pp. 2687-2700 ◽  
Author(s):  
Changgeng Liu ◽  
Tianzeng Chen ◽  
Yongchun Liu ◽  
Jun Liu ◽  
Hong He ◽  
...  
Keyword(s):  
Oxidation State ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Organic N ◽  
Carbon Oxidation ◽  
Formation Processes ◽  
Aerosol Formation ◽  
Product Model ◽  
Seed Particles ◽  
Oxidized Products

Abstract. 2-Methoxyphenol (guaiacol) is derived from the lignin pyrolysis and taken as a potential tracer for wood smoke emissions. In this work, the effect of SO2 at atmospheric levels (0–56 ppbv) on secondary organic aerosol (SOA) formation and its oxidation state during guaiacol photooxidation was investigated in the presence of various inorganic seed particles (i.e., NaCl and (NH4)2SO4). Without SO2 and seed particles, SOA yields ranged from (9.46±1.71) % to (26.37±2.83) % and could be well expressed by a one-product model. According to the ratio of the average gas-particle partitioning timescale (τ‾g-p) over the course of the experiment to the vapor wall deposition timescale (τg−w), the determined SOA yields were underestimated by a factor of ∼2. The presence of SO2 resulted in enhancing SOA yield by 14.04 %–23.65 %. With (NH4)2SO4 and NaCl seed particles, SOA yield was enhanced by 23.07 % and 29.57 %, respectively, which further increased significantly to 29.78 %–53.43 % in the presence of SO2, suggesting that SO2 and seed particles have a synergetic contribution to SOA formation. The decreasing trend of the τ‾g-p/τg-w ratio in the presence of seed particles and SO2 suggested that more SOA-forming vapors partitioned into the particle phase, consequently increasing SOA yields. It should be noted that SO2 was found to be in favor of increasing the carbon oxidation state (OSC) of SOA, indicating that the functionalization or the partitioning of highly oxidized products into particles should be more dominant than the oligomerization. In addition, the average N∕C ratio of SOA was 0.037, which revealed that NOx participated in the photooxidation process, consequently leading to the formation of organic N-containing compounds. The experimental results demonstrate the importance of SO2 on the formation processes of SOA and organic S-containing compounds and are also helpful to further understand SOA formation from the atmospheric photooxidation of guaiacol and its subsequent impacts on air quality and climate.

scholarly journals Formation and aging of secondary organic aerosol from toluene: changes in chemical composition, volatility, and hygroscopicity

2015 ◽  
Vol 15 (14) ◽  
pp. 8301-8313 ◽  
Author(s):  
L. Hildebrandt Ruiz ◽  
A. L. Paciga ◽  
K. M. Cerully ◽  
A. Nenes ◽  
N. M. Donahue ◽  
...  
Keyword(s):  
Oxidation State ◽  
Secondary Organic Aerosol ◽  
Organic Aerosol ◽  
Clear Correlation ◽  
Carbon Oxidation ◽  
Mass Yield ◽  
Initial Formation ◽  
Chemical Aging ◽  
Photo Oxidation ◽  
Volatile Organic

Abstract. Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NOx under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OSc), and mass yield. The OA oxidation state generally increased during photo-oxidation, and the final OA OSc ranged from −0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. There was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.

scholarly journals Aircraft Observations of Aerosol in the Manaus Urban Plume and Surrounding Tropical Forest during GoAmazon 2014/15

2018 ◽  
Author(s):  
John E. Shilling ◽  
Mikhail S. Pekour ◽  
Edward C. Fortner ◽  
Paulo Artaxo ◽  
Suzane de Sá ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Oxidation State ◽  
Biomass Burning ◽  
Urban Pollution ◽  
Organic Aerosol ◽  
Dry Season ◽  
Carbon Oxidation ◽  
Wet Season ◽  
The Mean ◽  
American Cities

Abstract. The Green Ocean Amazon (GoAmazon 2014/5) campaign, conducted from January 2014–December 2015 in the vicinity of Manaus, Brazil, was designed to study the aerosol lifecycle and aerosol-cloud interactions in both pristine and anthropogenically-influenced conditions. As part of this campaign, the U.S. Department of Energy (DOE) G-1 research aircraft was deployed from February 17–March 25, 2014 (wet season) and September 6–October 5, 2014 (dry season) to investigate aerosol and cloud properties aloft. Here, we present results from the G-1 deployments focusing on measurements of the aerosol chemical composition and discussion of aerosol sources and secondary organic aerosol formation and aging. In the first portion of the manuscript, we provide an overview of the data and compare and contrast the data from the wet and dry season. Organic aerosol (OA) dominates the deployment-averaged chemical composition, comprising 78 % of the non-refractory PM1 aerosol mass with sulfate comprising 13 %, nitrate 5 %, and ammonium 4 %. This product distribution was unchanged between seasons, despite the fact that total aerosol loading was significantly higher in the dry season and that regional and local biomass burning was a significant source of OA mass in the dry, but not wet, season. However, the OA was more oxidized in the dry season, with the median of the mean carbon oxidation state increasing from −0.45 in the wet season to −0.02 in the dry season. In the second portion of the manuscript, we discuss the evolution of the Manaus plume on March 13, 2014, one of the golden days in the wet season. On this flight, we observe a clear increase in OA concentrations in the Manaus plume relative to the background. As the plume is transported downwind and ages, we observe dynamic changes in the OA. The mean carbon oxidation state of the OA increases from −0.6 to −0.45 during the 4–5 hours of photochemical aging. Hydrocarbon-like organic aerosol (HOA) mass is lost with ΔHOA/ΔCO values decreasing from 17.6 μg/m3 ppmv−1 over Manaus to 10.6 μg/m3 ppmv−1 95 km downwind. Loss of HOA is balanced out by formation of oxygenated organic aerosol (OOA) with ΔOOA/ΔCO increasing from 9.2 to 23.1 μg/m3 ppmv−1. Because HOA loss is balanced by OOA formation, we observe little change in the net Δorg/ΔCO values; Δorg/ΔCO averages 31 μg/m3 ppmv−1 and does not increase with aging. Our observation of constant Δorg/ΔCO are in contrast to literature studies of the outflow of several North American cities, which report significant increases in Δorg/ΔCO for the first day of plume aging. These observations suggest that SOA formation in the Manaus plume occurs, at least in part, by a different mechanism than observed in urban outflow plumes in most other literature studies. Constant Δorg/ΔCO with plume aging has been observed in many biomass burning plumes, but we are unaware of reports of fresh urban emissions aging in this manner. These observations show that urban pollution emitted from Manaus in the wet season forms much less particulate downwind than urban pollution emitted from North American cities.

scholarly journals Measurement of soil carbon oxidation state and oxidative ratio by13C nuclear magnetic resonance

2009 ◽  
Vol 114 (G2) ◽  
pp. n/a-n/a ◽  
Author(s):  
W. C. Hockaday ◽  
C. A. Masiello ◽  
J. T. Randerson ◽  
R. J. Smernik ◽  
J. A. Baldock ◽  
...  
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Soil Carbon ◽  
Oxidation State ◽  
Carbon Oxidation ◽  
Nuclear Magnetic

scholarly journals Modeling organic aerosol concentrations and properties during winter 2014 in the northwestern Mediterranean region

2018 ◽  
Author(s):  
Mounir Chrit ◽  
Karine Sartelet ◽  
Jean Sciare ◽  
Marwa Majdi ◽  
José Nicolas ◽  
...  
Keyword(s):  
Air Quality ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Oxidation State ◽  
Organic Aerosol ◽  
Single Step ◽  
Basis Set ◽  
Residential Heating ◽  
Volatile Organic ◽  
Northwestern Mediterranean

Abstract. Organic aerosols are measured at a remote site (Ersa) on Corsica Cape in the northwestern Mediterranean basin during the Chemistry-Aerosol Mediterranean Experiment (CharMEx) winter campaign of 2014, when high organic concentrations from anthropogenic origin are observed. This work aims at representing the observed organic aerosol concentrations and properties (oxidation state) using the air-quality model Polyphemus with a surrogate approach for secondary organic aerosol (SOA) formation. Because intermediate/semi-volatile organic compounds (I/S-VOC) are the main precursors of SOA at Ersa during the winter 2014, different parameterizations to represent the emission and ageing of I/S-VOC were implemented in the chemistry-transport model of the air-quality platform Polyphemus (different volatility distribution emissions, single-step oxidation vs multi-step oxidation within a Volatility Basis Set framework, inclusion of non-traditional volatile organic compounds NTVOC). Simulations using the different parameterizations are compared to each other and to the measurements (concentration and oxidation state). The high observed organic concentrations are well reproduced whatever the parameterizations. They are slightly under-estimated with most parameterizations, but they are slightly over-estimated when the ageing of NTVOC is taken into account. The volatility distribution at emissions influences more strongly the concentrations than the choice of the parameterization that may be used for ageing (single-step oxidation vs multi-step oxidation), stressing the importance of an accurate characterization of emissions. Assuming the volatility distribution of sectors other than residential heating to be the same as residential heating may lead to a strong under-estimation of organic concentrations. The observed organic oxidation and oxygenation states are strongly under-estimated in all simulations, even when a recently developed parameterization for modeling the ageing of I/S-VOC from residential heating is used. This suggests that uncertainties in the ageing of I/S-VOC emissions remain to be elucidated, with a potential role of organic nitrate from anthropogenic precursors and highly oxygenated organic molecules.

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