Secondary Organic Aerosol (SOA) formation from the β-pinene + NO&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt; system: effect of humidity and peroxy radical fate

Boyd, Christopher M.; Sánchez, Javier; Xu, Lu; Eugene, Alexis J.; Nah, Theodora; Tuet, Wing Y.; Guzmán, Marcelo I.; Ng, N. L.

doi:10.5194/acpd-15-2679-2015

Cited by 37 publications

(91 citation statements)

References 136 publications

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“…For these three oxidation channels, RH has little effect on SOA yields from OH channel oxidization. Previous studies have shown that humidity has little effect on SOA formation from NO 3 oxidation of alkenes (Bonn and Moorgat, 2002;Fry et al, 2009;Boyd et al, 2015). Thus, only the O 3 channel is greatly influenced by RH.…”

Section: Soa Yieldsmentioning

confidence: 93%

Different roles of water in secondary organic aerosol formation from toluene and isoprene

Jia

2018

Atmos. Chem. Phys.

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Abstract. Roles of water in the formation of secondary organic aerosol (SOA) from the irradiations of toluene-NO 2 and isoprene-NO 2 were investigated in a smog chamber. Experimental results show that the yield of SOA from toluene almost doubled as relative humidity increased from 5 to 85 %, whereas the yield of SOA from isoprene under humid conditions decreased by 2.6 times as compared to that under dry conditions. The distinct difference of RH effects on SOA formation from toluene and isoprene is well explained with our experiments and model simulations. The increased SOA from humid toluene-NO 2 irradiations is mainly contributed by O-H-containing products such as polyalcohols formed from aqueous reactions. The major chemical components of SOA in isoprene-NO 2 irradiations are oligomers formed from the gas phase. SOA formation from isoprene-NO 2 irradiations is controlled by stable Criegee intermediates (SCIs) that are greatly influenced by water. As a result, high RH can obstruct the oligomerization reaction of SCIs to form SOA.

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Section: Soa Yieldsmentioning

confidence: 93%

Different roles of water in secondary organic aerosol formation from toluene and isoprene

Jia

2018

Atmos. Chem. Phys.

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“…Gas-phase production with dynamic gas-particle partitioning followed by rapid loss, such as by photolysis (28,29), heterogeneous hydrolysis (30)(31)(32)(33), or reaction with the hydroxyl radical (OH) (34,35), could potentially operate on such timescales and have different patterns as a function of time of day between the C 5 and C 10 groups. We note that the volatile organic compound + NO 3 and RO 2 + NO reactions produce varying levels of primary/secondary vs. tertiary ONs, all of which having different hydrolysis rates (30,32,33). Thus, the overall contribution of the various loss pathways to pON lifetime warrants additional studies.…”

Section: Resultsmentioning

confidence: 99%

Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

Lee

Mohr

Lopez‐Hilfiker

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

300

438

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Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene-and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gasparticle equilibrium and (ii) have a short particle-phase lifetime (∼2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment. O rganic nitrates (ONs; ON = RONO 2 + RO 2 NO 2 ) are an important reservoir, if not sink, of atmospheric nitrogen oxides (NO x = NO + NO 2 ). ONs formed from isoprene oxidation alone are responsible for the export of 8-30% of anthropogenic NO x out of the US continental boundary layer (1, 2). Regional NO x budgets and tropospheric ozone (O 3 ) production are, therefore, particularly sensitive to uncertainties in the yields and fates of ON (3-6). The yields implemented in modeling studies are determined from laboratory experiments, in which only a few of the first generation gaseous ONs or the total gas-phase ONs and particle-phase organic nitrates (pONs) have been quantified, whereas production of highly functionalized ONs capable of strongly partitioning to the particle phase have been inferred (7-11) or directly measured in the gas phase (12). Addition of a nitrate (-ONO 2 ) functional group to a hydrocarbon is estimated to lower the equilibrium saturation vapor pressure by 2.5-3 orders of magnitude (13). Thus, ON formation can enhance particle-phase partitioning of semivolatile species in regions with elevated levels of nitrogen oxides, contributing to secondary organic aerosol (SOA) growth (8). However, highly time-resolved measurements of speciated ON in the particle phase have been lacking.We use a recently developed high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS) using iodide-adduct ionization (14) with a filter inlet for gases and aerosols (FIGAERO) (15) that allows alternating in situ measurements of the molecular SignificanceWe present online field observations of the speciated molecular composition of organic nitrates in ambient atmospheric particles utilizing recently developed high-resolution MS-based instrumentation. We find that never-before-identified low-volatility organi...

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“…The contribution of particulate organic nitrates (pON) to measured nitrate has been estimated using the method described in Fry et al (2009) for the SEAC 4 RS flights on which the HR-ToF-AMS was operated . The pON, likely in the form of oxidized monoterpene nitrates (Boyd et al, 2015;Draper et al, 2015;Xu et al, 2015a, b), is estimated to be between 15 and 40 % of the total measured nitrate above the surface in the well-mixed and transition layers, and more than 63 % across the southeastern US at the surface (Xu et al, 2015a). However, nitrate represented < 5 % of fine aerosol mass in the data analyzed here.…”

Section: A Brock Et Al: Aerosol Optical Properties In the Southementioning

confidence: 99%

Aerosol optical properties in the southeastern United States in summer – Part 1: Hygroscopic growth

et al. 2016

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Abstract. Aircraft observations of meteorological, trace gas, and aerosol properties were made during MaySeptember 2013 in the southeastern United States (US) under fair-weather, afternoon conditions with well-defined planetary boundary layer structure. Optical extinction at 532 nm was directly measured at relative humidities (RHs) of ∼ 15, ∼ 70, and ∼ 90 % and compared with extinction calculated from measurements of aerosol composition and size distribution using the κ-Köhler approximation for hygroscopic growth. The calculated enhancement in hydrated aerosol extinction with relative humidity, f (RH), calculated by this method agreed well with the observed f (RH) at ∼ 90 % RH. The dominance of organic aerosol, which comprised 65 ± 10 % of particulate matter with aerodynamic diameter < 1 µm in the planetary boundary layer, resulted in relatively low f (RH) values of 1.43 ± 0.67 at 70 % RH and 2.28 ± 1.05 at 90 % RH. The subsaturated κ-Köhler hygroscopicity parameter κ for the organic fraction of the aerosol must have been < 0.10 to be consistent with 75 % of the observations within uncertainties, with a best estimate of κ = 0.05. This subsaturated κ value for the organic aerosol in the southeastern US is broadly consistent with field studies in rural environments. A new, physically based, single-parameter representation was developed that better described f (RH) than did the widely used gamma power-law approximation.

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Secondary Organic Aerosol (SOA) formation from the β-pinene + NO<sub>3</sub> system: effect of humidity and peroxy radical fate

Cited by 37 publications

References 136 publications

Different roles of water in secondary organic aerosol formation from toluene and isoprene

Different roles of water in secondary organic aerosol formation from toluene and isoprene

Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

Aerosol optical properties in the southeastern United States in summer – Part 1: Hygroscopic growth

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