HOx and NOx production in oxidation flow reactors via photolysis of isopropyl nitrite, isopropyl nitrite-d7, and 1,3-propyl dinitrite at λ = 254, 350, and 369 nm

Lambe, Andrew T.; Krechmer, Jordan E.; Peng, Zhe; Casar, Jason R.; Carrasquillo, A. J.; Raff, Jonathan D.; Jimenez, José L.; Worsnop, Douglas R.

doi:10.5194/amt-2018-225

Cited by 4 publications

(5 citation statements)

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“…We have presented an experimental technique where particle growth can be studied with variable OH levels such that the OH exposure ([OH] times residence time) to oxidation products can be kept below 10 9 molecule cm –3 s. Our technique is akin to the oxidation flow reactor , but runs under modest oxidation rates and moderate NO levels. SOA yields were derived based on comparison to the growth of seed particles due to SO 2 photooxidation.…”

Section: Discussionmentioning

confidence: 99%

Particle Formation from Photooxidation of αpinene, Limonene, and Myrcene

et al. 2022

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We present measurements of the effect of first-generation secondary organic aerosol (SOA) material on the growth of ∼10 nanometer diameter seed particles composed of sulfuric acid and water. Experiments were performed in an atmospheric pressure, vertically aligned flow reactor where OH was produced from HONO photolysis in the presence of either SO 2 or a monoterpene. For typical conditions, organic compounds at ∼300 ppbv are exposed to photooxidation for a time of ∼80 s at a [OH] of about 6 × 10 6 cm −3 : thus, oxidation products have minimal OH exposure. The measured size changes of the sulfuric acid seed particles can then be attributed to the uptake of firstgeneration products. Along with descriptions of the apparatus and the procedure, the analysis to obtain SOA yields by comparing them to growth with H 2 SO 4 (g) is detailed. Results from photooxidation experiments of αpinene, limonene, and myrcene give SOA yields of 0.040, 0.084, and 0.16, respectively. These SOA yields roughly double with each addition of a double bond to the compound. The αpinene and limonene results are in accord with the results of many previous SOA experiments, while the myrcene SOA yield stands alone. Photooxidation of myrcene also led to significant nucleation, and the species responsible is comparable to H 2 SO 4 at a 35% relative humidity in its nucleation capability.

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Section: Discussionmentioning

confidence: 99%

Particle Formation from Photooxidation of αpinene, Limonene, and Myrcene

et al. 2022

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“…The corresponding actinic flux ranged from approximately 1 × 10 14 to 3 × 10 15 photons cm −2 s −1 . 26,28 2.1. Oxidant Generation.…”

Section: Methodsmentioning

confidence: 99%

“…The ultraviolet (UV) irradiance was measured using a photodetector (TOCON-GaP6, sglux GmbH) and was varied across different experiments by changing the control voltage applied to the ballast between 1.5 and 10 volts of direct current (VDC). The corresponding actinic flux ranged from approximately 1 × 10 14 to 3 × 10 15 photons cm –2 s –1 . , …”

Section: Experimental Sectionmentioning

confidence: 99%

Comparison of the Yield and Chemical Composition of Secondary Organic Aerosol Generated from the OH and Cl Oxidation of Decamethylcyclopentasiloxane

Avery

Alton

Canagaratna

et al. 2023

ACS Earth Space Chem.

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Cyclic volatile methyl siloxanes (cVMS) that are emitted from industrial processes and consumer products often dominate the burden of volatile organic compounds (VOCs) in occupied spaces. cVMS may contribute to oxygenated VOC and secondary organic aerosol (SOA) formation following oxidation by gas-phase radicals in both indoor and outdoor source regions. Several recent studies examined the SOA formation potential of decamethylcyclopentasiloxane (D 5 ) following exposure to hydroxyl radicals (OH) and found that this reaction generates SOA in high yield following multiple days of oxidative aging. Chlorine atoms (Cl) may compete with OH for the oxidative loss of D 5 in indoor and outdoor source regions with active chlorine chemistry, but the SOA formation potential of D 5 + Cl reactions has not been studied. Here, we characterized the yield and chemical composition of SOA generated from Cl oxidation of D 5 in an oxidation flow reactor (OFR) under dry [relative humidity (RH) < 5%] and humid (RH = 40%) conditions and compared results to the yield and composition of SOA generated from OH oxidation of D 5 . D 5 was oxidized using integrated OH and Cl exposures (OH exp and Cl exp ) ranging from 1.1 × 10 12 to 8.2 × 10 12 cm −3 s and from 1.6 × 10 10 to 1.6 × 10 12 cm −3 s, respectively. Like OH, Cl facilitated multistep SOA oxidative aging over the range of OFR conditions that were studied, with maximum SOA mass yields of 1.5 and 1.3 obtained following OH and Cl oxidation of D 5 under humid conditions. These results suggest that indoor and outdoor source regions that are significantly influenced by chlorine chemistry may enhance the atmospheric SOA formation potential of D 5 .

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“…When SOA contributed by unexplained S/IVOCs was further estimated, 75%–100% formed SOA in OFR can be explained, emphasizing the important contribution from ambient S/IVOC species to SOA. Investigating SOA formation under an expanded set of variable and high-NO x OFR photochemical conditions using methods described in Lambe et al. , and Peng et al will be performed in future studies.…”

Section: Implication Of This Studymentioning

confidence: 99%

Oxidation Flow Reactor Results in a Chinese Megacity Emphasize the Important Contribution of S/IVOCs to Ambient SOA Formation

Zhou

Chen

et al. 2021

Environ. Sci. Technol.

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Oxygenated volatile organic compounds (OVOCs) and secondary organic aerosol (SOA) formation potential of ambient air in Guangzhou, China was investigated using a field-deployed oxidation flow reactor (OFR). The OFR was used to mimic hours to weeks of atmospheric exposure to hydroxyl (OH) radicals within the 2–3 min residence time. A comprehensive investigation on the variation of VOCs and OVOCs as a function of OH exposure is shown. Substantial formation of organic acids and nitrogen-containing OVOC species were observed. Maximum SOA formation in the OFR was observed following 1–4 equiv days’ OH exposure. SOA produced from known/measured VOC/IVOC precursors such as single-ring aromatics and long-chain alkanes can account for 52–75% of measured SOA under low NO x and 26–60% under high NO x conditions based on laboratory SOA yield parametrizations. To our knowledge, this is the first time that the contribution (8–20%) of long-chain (C8–C20) alkane oxidation to OFR SOA formation was quantified from direct measurement. By additionally estimating contribution from unmeasured semivolatile and intermediate volatility compounds (S/IVOCs) that are committed with C8–C20 alkanes, 64–100% of the SOA formation observed in the OFR can be explained, signifying the important contribution of S/IVOCs such as large cyclic alkanes to ambient SOA.

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HO_x and NO_x production in oxidation flow reactors via photolysis of isopropyl nitrite, isopropyl nitrite-d₇, and 1,3-propyl dinitrite at λ = 254, 350, and 369 nm

Cited by 4 publications

References 35 publications

Particle Formation from Photooxidation of αpinene, Limonene, and Myrcene

Particle Formation from Photooxidation of αpinene, Limonene, and Myrcene

Comparison of the Yield and Chemical Composition of Secondary Organic Aerosol Generated from the OH and Cl Oxidation of Decamethylcyclopentasiloxane

Oxidation Flow Reactor Results in a Chinese Megacity Emphasize the Important Contribution of S/IVOCs to Ambient SOA Formation

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