Aerosol Liquid Water Driven by Anthropogenic Nitrate: Implications for Lifetimes of Water-Soluble Organic Gases and Potential for Secondary Organic Aerosol Formation

Abstract. The lightest Non Methane HydroCarbon (NMHC), i.e., acetylene (C2H2) is found to form secondary organic aerosol (SOA). Contrary to current belief, the number of carbon atoms, n, for a NMHC to act as SOA precursor is lowered to n=2 here. The OH-radical initiated oxidation of C2H2 forms glyoxal (CHOCHO) as the highest yield product, and >99% of the SOA from C2H2 is attributed to CHOCHO. SOA formation from C2H2 and CHOCHO was studied in a photochemical and a dark simulation chamber. Further, the experimental conditions were varied with respect to the chemical composition of the seed aerosols, mild acidification with sulphuric acid (SA, 3<pH<4), and relative humidity (10<RH<90%). The rate of SOA formation is found enhanced by several orders of magnitude in the photochemical system. The SOA yields (YSOA) ranged from 1% to 24% and did not correlate with the organic mass portion of the seed, but increased linearly with liquid water content (LWC) of the seed. For fixed LWC, YSOA varied by more than a factor of five. Water soluble organic carbon (WSOC) photochemistry in the liquid water associated with internally mixed inorganic/WSOC seed aerosols is found responsible for this seed effect. WSOC photochemistry enhances the SOA source from CHOCHO, while seeds containing amino acids (AA) and/or SA showed among the lowest of all YSOA values, and largely suppress the photochemical enhancement on the rate of CHOCHO uptake. Our results give first evidence for the importance of heterogeneous photochemistry of CHOCHO in SOA formation, and identify a potential bias in the currently available YSOA data for other SOA precursor NMHCs. We demonstrate that SOA formation via the aqueous phase is not limited to cloud droplets, but proceeds also in the absence of clouds, i.e., does not stop once a cloud droplet evaporates. Atmospheric models need to be expanded to include SOA formation from WSOC photochemistry of CHOCHO, and possibly other α-dicarbonyls, in aqueous aerosols.

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Secondary organic aerosol formation from acetylene (C2H2): seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-8-14841-2008 ◽

2008 ◽

Vol 8 (4) ◽

pp. 14841-14892 ◽

Cited By ~ 11

Author(s):

R. Volkamer ◽

P. J. Ziemann ◽

M. J. Molina

Keyword(s):

Aqueous Phase ◽

Liquid Water ◽

Secondary Organic Aerosol ◽

Cloud Droplet ◽

Organic Aerosol ◽

Liquid Water Content ◽

Water Soluble ◽

Aerosol Formation ◽

Cloud Droplets ◽

Experimental Conditions

Abstract. The lightest Non Methane HydroCarbon (NMHC), i.e. acetylene (C2H2) is found to form secondary organic aerosol (SOA). Contrary to current belief, the number of carbon atoms, n, for a NMHC to act as SOA precursor is lowered to n=2 here. The OH-radical initiated oxidation of C2H2 forms glyoxal (CHOCHO) as the highest yield product, and >99% of the SOA from C2H2 is attributed to CHOCHO. SOA formation from C2H2 and CHOCHO was studied in a photochemical and a dark simulation chamber. Further, the experimental conditions were varied with respect to the chemical composition of the seed aerosol, mild acidification with sulphuric acid (SA, 3<pH<4), and relative humidity (10<RH<90%). The rate of SOA formation is found enhanced by several orders of magnitude in the photochemical system. The SOA yields (YSOA) ranged from 1% to 20% and did not correlate with the organic mass portion of the seed, but increased linearly with liquid water content (LWC) of the seed. For fixed LWC, YSOA varied by more than a factor of five. Water soluble organic carbon (WSOC) photochemistry in the liquid water associated with internally mixed inorganic/WSOC seed aerosols is found responsible for this seed effect. WSOC photochemistry enhances the SOA source from CHOCHO, while seeds containing amino acids (AA) and/or SA showed among the lowest of all YSOA values, and largely suppress the photochemical enhancement on the rate of CHOCHO uptake. Our results give first evidence for the importance of heterogeneous photochemistry of CHOCHO in SOA formation, and identify a potential bias in the currently available YSOA data for other SOA precursor NMHCs. We demonstrate that SOA formation via the aqueous phase is not limited to cloud droplets, but proceeds also in the absence of clouds, i.e. does not stop once a cloud droplet evaporates. Atmospheric models need to be expanded to include SOA formation from WSOC photochemistry of CHOCHO, and possibly other α-dicarbonyls, in aqueous aerosols.

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Role of Aerosol Liquid Water in Secondary Organic Aerosol Formation from Volatile Organic Compounds

Environmental Science & Technology ◽

10.1021/acs.est.6b04700 ◽

2017 ◽

Vol 51 (3) ◽

pp. 1405-1413 ◽

Cited By ~ 47

Author(s):

Jennifer A. Faust ◽

Jenny P. S. Wong ◽

Alex K. Y. Lee ◽

Jonathan P. D. Abbatt

Keyword(s):

Volatile Organic Compounds ◽

Organic Compounds ◽

Liquid Water ◽

Secondary Organic Aerosol ◽

Organic Aerosol ◽

Aerosol Formation ◽

Volatile Organic ◽

Secondary Organic Aerosol Formation

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Secondary organic aerosol formation from biomass burning emissions

10.5194/acp-2019-326 ◽

2019 ◽

Cited By ~ 2

Author(s):

Christopher Y. Lim ◽

David H. Hagan ◽

Matthew M. Coggon ◽

Abigail R. Koss ◽

Kanako Sekimoto ◽

...

Keyword(s):

Biomass Burning ◽

Secondary Organic Aerosol ◽

Total Concentration ◽

Organic Aerosol ◽

Oh Radicals ◽

Aerosol Formation ◽

Atmospheric Aging ◽

Aerosol Mass ◽

Photochemical Aging ◽

Organic Gases

Abstract. Biomass burning is an important source of aerosol and trace gases to the atmosphere, but how these emissions change chemically during their lifetimes is not fully understood. As part of the Fire Influence on Regional and Global Environments Experiment (FIREX 2016), we investigated the effect of photochemical aging on biomass burning organic aerosol (BBOA), with a focus on fuels from the western United States. Emissions were sampled into a small (150 L) environmental chamber and photochemically aged via the addition of ozone and irradiation by 254 nm light. While some fraction of species undergoes photolysis, the vast majority of aging occurs via reaction with OH radicals, with total OH exposures corresponding to the equivalent of up to 10 days of atmospheric oxidation. For all fuels burned, large and rapid changes are seen in the ensemble chemical composition of BBOA, as measured by an aerosol mass spectrometer (AMS). Secondary organic aerosol (SOA) formation is seen for all aging experiments and continues to grow with increasing OH exposure, but the magnitude of the SOA formation is highly variable between experiments. This variability can be explained well by a combination of experiment-to-experiment differences in OH exposure and the total concentration of non-methane organic gases (NMOGs) in the chamber before oxidation, measured by PTR-ToF-MS (r2 values from 0.64 to 0.83). From this relationship, we calculate the fraction of carbon from biomass burning NMOGs that is converted to SOA as a function of equivalent atmospheric aging time, with carbon yields ranging from 24 ± 4 % after 6 hours to 56 ± 9 % after 4 days.

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