Transitions from Functionalization to Fragmentation Reactions of Laboratory Secondary Organic Aerosol (SOA) Generated from the OH Oxidation of Alkane Precursors

Lambe, Andrew T.; Onasch, T. B.; Croasdale, D. R.; Wright, Justin P.; Martin, Alexander; Franklin, J. P.; Massoli, P.; Kroll, J. H.; Canagaratna, Manjula R.; Brune, William H.; Worsnop, Douglas R.; Davidovits, P.

doi:10.1021/es300274t

Cited by 201 publications

(292 citation statements)

References 56 publications

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“…Given the Van Krevelen diagram analysis described above in section 3.2.2, fragmentations reactions appear not to be the dominant oxidation pathway. This conclusion is consistent with the recent work of Lambe et al [2012] that showed that for larger alkanes, the onset of fragmentation occurs at an O : C of about 0.3, which is much higher than the O : C of HOA reported here (0.14). For functionalization reactions, based on the OM : OC ratio of 1.3 for HOA and an estimated OM : OC of 1.2 for an un-oxidized alkane chain, it is calculated that the increase in HOA mass due to oxidation is only 8%, which is smaller than the standard deviation (21%) of the data shown in Figure 8.…”

Section: The Quantitative Dependence Of Secondary Organicsupporting

confidence: 94%

Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

et al. 2013

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Organic aerosols (OA) in Pasadena are characterized using multiple measurements from the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign. Five OA components are identified using positive matrix factorization including hydrocarbon‐like OA (HOA) and two types of oxygenated OA (OOA). The Pasadena OA elemental composition when plotted as H : C versus O : C follows a line less steep than that observed for Riverside, CA. The OOA components from both locations follow a common line, however, indicating similar secondary organic aerosol (SOA) oxidation chemistry at the two sites such as fragmentation reactions leading to acid formation. In addition to the similar evolution of elemental composition, the dependence of SOA concentration on photochemical age displays quantitatively the same trends across several North American urban sites. First, the OA/ΔCO values for Pasadena increase with photochemical age exhibiting a slope identical to or slightly higher than those for Mexico City and the northeastern United States. Second, the ratios of OOA to odd‐oxygen (a photochemical oxidation marker) for Pasadena, Mexico City, and Riverside are similar, suggesting a proportional relationship between SOA and odd‐oxygen formation rates. Weekly cycles of the OA components are examined as well. HOA exhibits lower concentrations on Sundays versus weekdays, and the decrease in HOA matches that predicted for primary vehicle emissions using fuel sales data, traffic counts, and vehicle emission ratios. OOA does not display a weekly cycle—after accounting for differences in photochemical aging —which suggests the dominance of gasoline emissions in SOA formation under the assumption that most urban SOA precursors are from motor vehicles.

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Section: The Quantitative Dependence Of Secondary Organicsupporting

confidence: 94%

Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

et al. 2013

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“…At the extreme oxidant exposures used in the present study, fragmentation reactions (CÀ ÀC bond cleavage, Ng et al 2011a) may begin to form lower-volatility products, reducing the observed emission factors (Lambe et al 2012). The importance of fragmentation reactions may be lower for cyclic organics such as levoglucosan (for which CÀ ÀC bond cleavage does not split the molecule), which are contained in large amounts in wood-burning OM (Shafizadeh 1985;Rogge et al 1998;Simoneit et al 1999;Fine et al 2001;Graham et al 2002).…”

Section: Wood-stove Emission Factorsmentioning

confidence: 76%

Organic Emissions from a Wood Stove and a Pellet Stove Before and After Simulated Atmospheric Aging

Corbin

Keller

Lohmann

et al. 2015

Aerosol Science and Technology

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Logwood and pellet stoves are popular heating sources around the world. The particulate matter emitted from such stoves contains organic particulate matter (OM), soot, and ash, each of which may have significant effects on climate and health. In this study, the primary OM (POM) emitted from a wood stove and a pellet stove operated according to standard Swiss testing protocols were characterized using aerosol mass spectrometry. The POM mass spectra were found to be highly reproducible, and contained CO C as the dominant ion. Because the POM emitted by such stoves is typically enhanced by the condensation of gaseous organics following atmospheric aging, the secondary OM (SOM) formation potential of these stoves was simulated using the Micro Smog Chamber (MSC) designed by Keller and Burtscher in 2012. In general, OM emission factors from MSCaged aerosols were comparable to lower-time-resolution results from the literature, although the MSC exposed aerosols to much higher concentrations of oxidants and therefore produced OM that was more oxidized than expected for atmospheric samples. In addition, the logwood-stove particles remained highly aspherical even after oxidation, indicating that mixing with an external aerosol is required for these particles to become spherical. The one exception to this observation occurred when the wood failed to ignite and appeared to generate tar-ball OM particles.

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“…The yields, composition, and properties of the SOA depend not only on alkane structure, however, but also on the extent of aging of the product mixture via OH radical oxidation and nonoxidative heterogeneous/multiphase reactions. Whereas recent studies have investigated the effects of aging on the yield, volatility, and oxidation state of SOA formed from alkanes in the presence (Bahreini et al 2012;Tkacik et al 2012) and absence Lambe et al 2012;Yee et al 2012) of NO x , to our knowledge only the studies by Yee et al (2012) and Craven et al (2012) of the reaction of n-dodecane in the absence of NO x has identified specific reaction products and mechanisms responsible for SOA aging. Here, we report the results of a study that employed particle mass spectrometry, TPTD, functional group analysis, elemental analysis, and measurements of SOA yields to investigate the chemistry of SOA formation from the reaction of OH radicals with n-pentadecane (the C 15 n-alkane IVOC) in the presence of NO x , and the mechanisms by which aging alters the molecular composition and volatility of the SOA.…”

Section: Introductionmentioning

confidence: 99%

Chemical Mechanisms of Aging of Aerosol Formed from the Reaction ofn-Pentadecane with OH Radicals in the Presence of NO_x

Aimanant

Ziemann

2013

Aerosol Science and Technology

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The effects of aging via gas-phase oxidation and heterogeneous/multiphase reactions on the composition and volatility of secondary organic aerosol (SOA) were investigated in a series of environmental chamber experiments. SOA was formed from the reaction of n-pentadecane, a C 15 intermediate volatility alkane, with OH radicals in the presence of NO x under conditions corresponding to ∼1.5 and ∼15 h of daytime oxidation, and analyzed using a suite of real-time and offline methods. Functional group analysis indicated that the average number of nitrate, hydroxyl, carbonyl, carboxyl, ester, acylperoxynitrate, and methylene groups per C 15 molecule were 0.84, 1.07, 0.25, 0.00, 0.00, 0.00, and 12.84 in less aged SOA and 1.25, 0.69, 0.32, 0.00, 0.33, 0.10, and 12.27 in more aged SOA, and the corresponding O/C, H/C, and N/C ratios determined by offline elemental analysis were 0.32, 2.20, and 0.062, and 0.31, 1.86, and 0.061, respectively, similar to each other and in good agreement with values calculated from functional group composition. Time-dependent SOA yields and temperatureprogrammed thermal desorption (TPTD) analysis showed that the more aged SOA was much less volatile and more chemically complex, and when combined with particle mass spectra indicated that the major SOA components included 1,4-hydroxynitrates, cyclic hemiacetals (CHA), cyclic hemiacetal nitrates (CHAN), and related compounds, as well as hemiacetal (HA) and acetal oligomers. The effects of aging on functional group composition were due primarily to dehydration of CHA and formation of second-and thirdgeneration products via gas-phase OH radical reactions, whereas SOA volatility was reduced primarily by enhanced formation of HA and acetal oligomers through heterogeneous/multiphase reactions involving these multigeneration products. These results can be explained using well-established gas-phase and heterogeneous/multiphase reaction mechanisms.

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Transitions from Functionalization to Fragmentation Reactions of Laboratory Secondary Organic Aerosol (SOA) Generated from the OH Oxidation of Alkane Precursors

Cited by 201 publications

References 56 publications

Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

Organic Emissions from a Wood Stove and a Pellet Stove Before and After Simulated Atmospheric Aging

Chemical Mechanisms of Aging of Aerosol Formed from the Reaction ofn-Pentadecane with OH Radicals in the Presence of NO_x

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Transitions from Functionalization to Fragmentation Reactions of Laboratory Secondary Organic Aerosol (SOA) Generated from the OH Oxidation of Alkane Precursors

Cited by 201 publications

References 56 publications

Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

Organic Emissions from a Wood Stove and a Pellet Stove Before and After Simulated Atmospheric Aging

Chemical Mechanisms of Aging of Aerosol Formed from the Reaction ofn-Pentadecane with OH Radicals in the Presence of NOx

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Product

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Chemical Mechanisms of Aging of Aerosol Formed from the Reaction ofn-Pentadecane with OH Radicals in the Presence of NO_x