Alkyl nitrate photochemistry during the tropospheric organic chemistry experiment

Worton, David R.; Reeves, Claire E.; Penkett, S. A.; Sturges, William T.; Slemr, J.; Oram, D. E.; Bandy, Brian; Bloss, William J.; Carslaw, Nicola; Davey, James; Emmerson, Kathryn M.; Gravestock, Thomas; Hamilton, Jacqueline F.; Heard, Dwayne E.; Hopkins, James R.; Hulse, Anne; Ingram, Trevor; Jacob, Mark; Lee, James; Leigh, R. J.; Lewis, Alastair C.; Monks, Paul S.; Smith, Stuart

doi:10.1016/j.atmosenv.2009.11.038

Cited by 24 publications

(35 citation statements)

References 52 publications

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“…The alkyl nitrate evolution time depends on the concentration of OH, [OH]. Recently, Hofzumahaus et al (2009) found that the [OH] in PRD region was unexpectedly high and could reach on the order of 1 Â 10 7 molecule cm À3 , about one order of magnitude higher than that adopted in previous studies (Simpson et al, 2003;Worton et al, 2010). It should be noted that [OH] on the order of 1 Â 10 5 e1 Â 10 6 molecule cm À3 is generally found in clean air, while [OH] on the order of 1 Â 10 7 molecule cm À3 characterises a highly polluted atmospheric environment.…”

Section: Alkyl Nitrate Evolutionmentioning

confidence: 93%

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VOCs and OVOCs distribution and control policy implications in Pearl River Delta region, China

Louie¹,

Ho²,

Tsang³

et al. 2013

Atmospheric Environment

133

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h i g h l i g h t s < The first and foremost large spatialetemporal VOCs grid study in the PRD region. < More detailed VOCs spatial emission characteristics were identified. < High OH concentration in PRD favoured fast reactions and ozone formation. < Ozone formation potential of VOCs and OVOCs were analysed. < Findings supported further control measures and policies formulation. a b s t r a c tAmbient air measurements of volatile organic compounds (VOCs) and oxygenated volatile organic compounds (OVOCs) were conducted and characterised during a two-year grid study in the Pearl River Delta (PRD) region of southern China. The present grid study pioneered the systematic investigation of the nature and characteristics of complex VOC and OVOC sources at a regional scale. The largest contributing VOCs, accounting over 80% of the total VOCs mixing ratio, were toluene, ethane, ethyne, propane, ethene, butane, benzene, pentane, ethylbenzene, and xylenes. Sub-regional VOC spatial characteristics were identified, namely: i) relatively fresh pollutants, consistent with elevated vehicular and industrial activities, around the PRD estuary; and ii) a concentration gradient with higher mixing ratios of VOCs in the west as compared with the eastern part of PRD. Based on alkyl nitrate aging determination, a high hydroxyl radical (OH) concentration favoured fast hydrocarbon reactions and formation of locally produced ozone. The photochemical reactivity analysis showed aromatic hydrocarbons and alkenes together consisted of around 80% of the ozone formation potential (OFP) among the key VOCs. We also found that the OFP from OVOCs should not be neglected since their OFP contribution was more than one-third of that from VOCs alone. These findings support the choice of current air pollution control policy which focuses on vehicular sources but warrants further controls. Industrial emissions and VOCs emitted by solvents should be the next targets for ground-level ozone abatement.

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Section: Alkyl Nitrate Evolutionmentioning

confidence: 93%

“…This information is particularly useful to determine whether the pollutants originated from local sources or from long-distance transport. The evolution time (t) for the air mass can be determined by assuming an initial ambient alkyl nitrates mixing ratio of zero (Bertman et al, 1995;Simpson et al, 2003;Worton et al, 2010).…”

Section: Alkyl Nitrate Evolutionmentioning

confidence: 99%

VOCs and OVOCs distribution and control policy implications in Pearl River Delta region, China

Louie¹,

Ho²,

Tsang³

et al. 2013

Atmospheric Environment

133

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“…In this study, the photochemical evolution of alkyl nitrates and their parent hydrocarbons was examined using a simplified sequential reaction model, which was developed by Bertman et al (1995) and subsequently has been applied in many previous studies (Reeves et al, 2007;Russo et al, 2010;Sun et al, 2018;Worton et al, 2010). Briefly, this sequential reaction model considers the OH oxidation of parent hydrocarbons as well as formation and loss of alkyl nitrates, including the rate constants and branching ratios of related reactions.…”

Section: Sequential Reaction Modelmentioning

confidence: 99%

Observations of C1–C5 alkyl nitrates in the Yellow River Delta, northern China: Effects of biomass burning and oil field emissions

Zhang

Sun

Zheng

et al. 2019

Science of The Total Environment

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“…This has been shown to also be the case at the Taunus Observatory (Thieser et al 2016). Our measurements of PNs are in the range of PAN or the sum of individual PAN mixing ratios observed in different urban-suburban locations (Roberts, 1990;Roberts et al, 2007;LaFranchi et al, 2009 tal alkyl nitrate burden at rural locations influenced by urban emissions up to a few hundred parts per trillion per volume were derived by summing the mixing ratio of individually measured alkyl nitrates (C1 up to C8) by gas chromatography technics (Flocke et al, 1991(Flocke et al, , 1998Russo et al, 2010;Worton et al, 2010). Recent developments in chemical ionization mass spectrometry have enabled measurement of more complex, multifunctional nitrates of biogenic origin and revealed the occasional presence of parts per billion per volume levels of the sum of measured alkyl nitrates (Beaver et al, 2012).…”

Section: No X and Organic Nitrates At The Taunus Observatorymentioning

confidence: 99%

Day and night-time formation of organic nitrates at a forested mountain site in south-west Germany

et al. 2017

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Abstract. We report in situ measurements of total peroxy nitrates ( PNs) and total alkyl nitrates ( ANs) in a forested-urban location at the top of the Kleiner Feldberg mountain in south-west Germany. The data, obtained using thermal dissociation cavity ring-down spectroscopy (TD-CRDS) in August-September 2011 (PARADE campaign) and July 2015 (NOTOMO campaign), represent the first detailed study of PNs and ANs over continental Europe. We find that a significant fraction of NO x (up to 75 %) is sequestered as organics nitrates at this site. Furthermore, we also show that the night-time production of alkyl nitrates by reaction of NO 3 with biogenic hydrocarbons is comparable to that from daytime OH-initiated oxidation pathways. The ANs / ozone ratio obtained during PARADE was used to derive an approximate average yield of organic nitrates at noon from the OH initiated oxidation of volatile organic compounds (VOCs) of ∼ 7 % at this site in 2011, which is comparable with that obtained from an analysis of VOCs measured during the campaign. A much lower AN yield, < 2 %, was observed in 2015, which may result from sampling air with different average air mass ages and thus different degrees of breakdown of assumptions used to derive the branching ratio, but it may also reflect a seasonal change in the VOC mixture at the site.

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Alkyl nitrate photochemistry during the tropospheric organic chemistry experiment

Cited by 24 publications

References 52 publications

VOCs and OVOCs distribution and control policy implications in Pearl River Delta region, China

VOCs and OVOCs distribution and control policy implications in Pearl River Delta region, China

Observations of C1–C5 alkyl nitrates in the Yellow River Delta, northern China: Effects of biomass burning and oil field emissions

Day and night-time formation of organic nitrates at a forested mountain site in south-west Germany

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