Chlorine-Initiated Oxidation of α-Pinene: Formation of Secondary Organic Aerosol and Highly Oxygenated Organic Molecules

Author(s):  
Catherine G. Masoud ◽  
Lea Hildebrandt Ruiz
2017 ◽  
Author(s):  
Adrian M. Maclean ◽  
Christopher L. Butenhoff ◽  
James W. Grayson ◽  
Kelley Barsanti ◽  
Jose L. Jimenez ◽  
...  

Abstract. When simulating the formation and life cycle of secondary organic aerosol (SOA) with chemical transport models, it is often assumed that organic molecules are well mixed within SOA particles on the time scale of 1 h. While this assumption has been debated vigorously in the literature, the issue remains unresolved in part due to a lack of information on the mixing times within SOA particles as a function of both temperature and relative humidity. Using laboratory data, meteorological fields and a chemical transport model, we determine how often mixing times are


2019 ◽  
Vol 19 (3) ◽  
pp. 1491-1503 ◽  
Author(s):  
Dagny A. Ullmann ◽  
Mallory L. Hinks ◽  
Adrian M. Maclean ◽  
Christopher L. Butenhoff ◽  
James W. Grayson ◽  
...  

Abstract. Viscosities and diffusion rates of organics within secondary organic aerosol (SOA) remain uncertain. Using the bead-mobility technique, we measured viscosities as a function of water activity (aw) of SOA generated by the ozonolysis of limonene followed by browning by exposure to NH3 (referred to as brown limonene SOA or brown LSOA). These measurements together with viscosity measurements reported in the literature show that the viscosity of brown LSOA increases by 3–5 orders of magnitude as the aw decreases from 0.9 to approximately 0.05. In addition, we measured diffusion coefficients of intrinsic fluorescent organic molecules within brown LSOA matrices using rectangular area fluorescence recovery after photobleaching. Based on the diffusion measurements, as the aw decreases from 0.9 to 0.33, the average diffusion coefficient of the intrinsic fluorescent organic molecules decreases from 5.5×10-9 to 7.1×10-13 cm2 s−1 and the mixing times of intrinsic fluorescent organic molecules within 200 nm brown LSOA particles increases from 0.002 to 14 s. These results suggest that the mixing times of large organics in the brown LSOA studied here are short (<1 h) for aw and temperatures often found in the planetary boundary layer (PBL). Since the diffusion coefficients and mixing times reported here correspond to SOA generated using a high mass loading (∼1000 µg m−3), biogenic SOA particles found in the atmosphere with mass loadings ≤10 µg m−3 are likely to have higher viscosities and longer mixing times (possibly 3 orders of magnitude longer). These new measurements of viscosity and diffusion were used to test the accuracy of the Stokes–Einstein relation for predicting diffusion rates of organics within brown LSOA matrices. The results show that the Stokes–Einstein equation gives accurate predictions of diffusion coefficients of large organics within brown LSOA matrices when the viscosity of the matrix is as high as 102 to 104 Pa s. These results have important implications for predicting diffusion and mixing within SOA particles in the atmosphere.


2018 ◽  
Author(s):  
Dagny A. Ullmann ◽  
Mallory L. Hinks ◽  
Adrian Maclean ◽  
Christopher Butenhoff ◽  
James Grayson ◽  
...  

Abstract. Viscosities and diffusion rates of organics within secondary organic aerosol (SOA) remain uncertain. Using the bead-mobility technique, we measured the viscosities as a function of water activity (aw) of SOA generated by the ozonolysis of limonene followed by browning by exposure to NH3 (referred to as brown limonene SOA or brown LSOA). These measurements together with viscosity measurements reported in the literature show that the viscosity of brown LSOA increases by 3–5 orders of magnitude as the aw decreases from 0.9 to approximately 0.05. In addition, we measured diffusion coefficients of intrinsic fluorescent organic molecules within brown LSOA matrices using rectangular area fluorescence recovery after photobleaching. Based on the diffusion measurements, as the aw decreases from 0.9 to 0.33, the average diffusion coefficient of the intrinsic fluorescent organic molecules decreases from 5.5∙10-9 cm2 s-1 to 7.1∙10-13 cm2 s-1 and the mixing times of intrinsic fluorescent organic molecules within 200 nm brown LSOA particles increases from 0.002 s to 14 s. These results suggest that the mixing times of large organics in the brown LSOA studied here are short (


2020 ◽  
Vol 20 (2) ◽  
pp. 1183-1199 ◽  
Author(s):  
Meredith Schervish ◽  
Neil M. Donahue

Abstract. Gas-phase autoxidation of organics can generate highly oxygenated organic molecules (HOMs) and thus increase secondary organic aerosol production and enable new-particle formation. Here we present a new implementation of the volatility basis set (VBS) that explicitly resolves peroxy radical (RO2) products formed via autoxidation. The model includes a strong temperature dependence for autoxidation as well as explicit termination of RO2, including reactions with NO, HO2, and other RO2. The RO2 cross-reactions can produce dimers (ROOR). We explore the temperature and NOx dependence of this chemistry, showing that temperature strongly influences the intrinsic volatility distribution and that NO can suppress autoxidation under conditions typically found in the atmosphere.


2019 ◽  
Vol 10 (19) ◽  
pp. 5902-5908 ◽  
Author(s):  
Kristian J. Kiland ◽  
Adrian M. Maclean ◽  
Saeid Kamal ◽  
Allan K. Bertram

2016 ◽  
Vol 18 (13) ◽  
pp. 8785-8793 ◽  
Author(s):  
Mallory L. Hinks ◽  
Monica V. Brady ◽  
Hanna Lignell ◽  
Mijung Song ◽  
James W. Grayson ◽  
...  

This work explores the effect of environmental conditions on the photodegradation rates of atmospherically relevant, photolabile, organic molecules embedded in a film of viscous secondary organic material (SOM).


2017 ◽  
Vol 17 (21) ◽  
pp. 13037-13048 ◽  
Author(s):  
Adrian M. Maclean ◽  
Christopher L. Butenhoff ◽  
James W. Grayson ◽  
Kelley Barsanti ◽  
Jose L. Jimenez ◽  
...  

Abstract. When simulating the formation and life cycle of secondary organic aerosol (SOA) with chemical transport models, it is often assumed that organic molecules are well mixed within SOA particles on the timescale of 1 h. While this assumption has been debated vigorously in the literature, the issue remains unresolved in part due to a lack of information on the mixing times within SOA particles as a function of both temperature and relative humidity. Using laboratory data, meteorological fields, and a chemical transport model, we estimated how often mixing times are  < 1 h within SOA in the planetary boundary layer (PBL), the region of the atmosphere where SOA concentrations are on average the highest. First, a parameterization for viscosity as a function of temperature and RH was developed for α-pinene SOA using room-temperature and low-temperature viscosity data for α-pinene SOA generated in the laboratory using mass concentrations of  ∼ 1000 µg m−3. Based on this parameterization, the mixing times within α-pinene SOA are  < 1 h for 98.5 % and 99.9 % of the occurrences in the PBL during January and July, respectively, when concentrations are significant (total organic aerosol concentrations are  > 0.5 µg m−3 at the surface). Next, as a starting point to quantify how often mixing times of organic molecules are  < 1 h within α-pinene SOA generated using low, atmospherically relevant mass concentrations, we developed a temperature-independent parameterization for viscosity using the room-temperature viscosity data for α-pinene SOA generated in the laboratory using a mass concentration of  ∼ 70 µg m−3. Based on this temperature-independent parameterization, mixing times within α-pinene SOA are  < 1 h for 27 and 19.5 % of the occurrences in the PBL during January and July, respectively, when concentrations are significant. However, associated with these conclusions are several caveats, and due to these caveats we are unable to make strong conclusions about how often mixing times of organic molecules are  < 1 h within α-pinene SOA generated using low, atmospherically relevant mass concentrations. Finally, a parameterization for viscosity of anthropogenic SOA as a function of temperature and RH was developed using sucrose–water data. Based on this parameterization, and assuming sucrose is a good proxy for anthropogenic SOA, 70 and 83 % of the mixing times within anthropogenic SOA in the PBL are  < 1 h for January and July, respectively, when concentrations are significant. These percentages are likely lower limits due to the assumptions used to calculate mixing times.


2019 ◽  
Author(s):  
Christopher Y. Lim ◽  
David H. Hagan ◽  
Matthew M. Coggon ◽  
Abigail R. Koss ◽  
Kanako Sekimoto ◽  
...  

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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