Volatile and intermediate-volatility organic compounds in sub-urban Paris: variability, origin and importance for SOA formation

Ait-Helal, W.; Borbon, A.; Sauvage, S.; Gouw, J. A. de; Colomb, A.; Gros, Valérie; Freutel, F.; Crippa, Monica; Afif, Charbel; Baltensperger, Urs; Beekmann, Matthias; Doussin, Jean‐François; Durand-Jolibois, R.; Fronval, Isabelle; Grand, N.; Léonardis, T.; Lopez, Morgan; Michoud, Vincent; Miet, K.; Perrier, S.; Prévôt, Andrê S. H.; Schneider, Johannes; Siour, Guillaume; Zapf, Pascal; Locoge, N.

doi:10.5194/acpd-14-4841-2014

Cited by 4 publications

(5 citation statements)

References 160 publications

(206 reference statements)

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“…The HONO concentration levels were variable, up to 500 ppt, with the averaged daytime maximum of 210 ppt at around 09:00 LT. Furthermore, a detailed discussion of VOC results at SIRTA observatory can be found in Ait-Helal et al (2012).…”

Section: Overview Of Measurement Resultsmentioning

confidence: 99%

“…The detection of the azo-dye formed was made by a High Performance Liquid Chromatography (HPLC) with detection by visible absorption at 540 nm. The instrument for nitrous acid measurement has been described in detail by Afif et al (2012). This instrument was calibrated before and after the campaign using nitrite liquid solutions at different concentrations.…”

Section: Stable Species Measurementsmentioning

confidence: 99%

“…In addition, samples collected every three hours on Charcoal cartridges and analysed later by a GC-FID (Detournay et al, 2011) enabled measurement of 20 VOCs from C 7 to C 16 . More details on VOC measurements can be found in Ait-Helal et al (2012).…”

Section: Stable Species Measurementsmentioning

confidence: 99%

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Radical budget analysis in a suburban European site during the MEGAPOLI summer field campaign

et al. 2012

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Chemical Ionisation Mass Spectrometer measurements of hydroxyl radical (OH) and the sum of hydroperoxy and organic peroxy (HO2+RO2) radicals were conducted during the MEGAPOLI summer field campaign at the SIRTA observatory near Paris, France, in July 2009. OH and (HO2+RO2) showed a typical diurnal variation with averaged daytime maxima values around 5×106 and 1.2×108 molecule cm−3, respectively. Simultaneously, a large number of ancillary measurements, such as NOx, O3, HONO, HCHO and other VOCs were also conducted. These data provide an opportunity to assess our understanding of the radical chemistry in a suburban environment by comparing the radical observations to calculations. First, OH mixing ratios were estimated by a simple Photo Stationary State (PSS) calculation. PSS calculations overestimate the OH mixing ratio by 50%, especially at NOx mixing ratios lower than 10 ppb, suggesting that some loss processes were missing in the calculation at low NOx. Then, a photochemical box model simulation based on the Master Chemical Mechanism (MCM) and constrained by ancillary measurements was run to calculate radical concentrations. Three different modelling procedures were tested, varying the way the unconstrained secondary species were estimated, to cope with the unavoidable lack of their measurements. They led to significant differences in simulated radical concentrations. OH and (HO2+RO2) concentrations estimated by two selected model version were compared with measurements. These versions of the model were chosen because they lead, respectively, to the higher and lower simulated radical concentrations and are thus the two extremes versions. The box model showed better results than PSS calculations, with a slight overestimation of 12% and 5%, for OH and (HO2+RO2) respectively, in average for the reference model, and an overestimation of approximately 20% for OH and an underestimation for (HO2+RO2) for the other selected model version. Thus, we can conclude from our study that OH and (HO2+RO2) radical levels agree on average with observations within the uncertainty range. Finally, an analysis of the radical budget, on a daily basis (06:00–18:00 UTC), indicates that HONO photolysis (~35%), O3 photolysis (~23%), and aldehydes and ketones photolysis (~16% for formaldehyde and 18% for others) are the main radical initiation pathways. According to the MCM modelling, the reactions of RO2 with NO2 (~19%), leading mainly to PAN formation, is a significant termination pathway in addition to the main net loss...

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Section: Overview Of Measurement Resultsmentioning

confidence: 99%

Section: Stable Species Measurementsmentioning

confidence: 99%

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Radical budget analysis in a suburban European site during the MEGAPOLI summer field campaign

et al. 2012

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“…Speciated IVOCs, such as polycyclic aromatic hydrocarbons, have been routinely measured in the atmosphere. − Atmospheric concentrations of speciated IVOCs are generally lower than VOCs , and speciated IVOCs appear to modestly contribute to SOA formation . However, the dominant fraction of atmospheric IVOCs is not resolved by traditional gas-chromatographic analysis.…”

Section: Introductionmentioning

confidence: 99%

“…7−10 Atmospheric concentrations of speciated IVOCs are generally lower than VOCs 9,10 and speciated IVOCs appear to modestly contribute to SOA formation. 11 However, the dominant fraction of atmospheric IVOCs is not resolved by traditional gas-chromatographic analysis. Instead it appears as an unresolved complex mixture (UCM) of coeluting compounds 9 because of the exponential increase in the number of constitutional isomers with increasing carbon number.…”

Section: ■ Introductionmentioning

confidence: 99%

Intermediate-Volatility Organic Compounds: A Large Source of Secondary Organic Aerosol

Zhao

Hennigan

May

et al. 2014

Environ. Sci. Technol.

259

403

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Secondary organic aerosol (SOA) is a major component of atmospheric fine particle mass. Intermediate-volatility organic compounds (IVOCs) have been proposed to be an important source of SOA. We present a comprehensive analysis of atmospheric IVOC concentrations and their SOA production using measurements made in Pasadena, California during the California at the Nexus of Air Quality and Climate Change (CalNex) study. The campaign-average concentration of primary IVOCs was 6.3 ± 1.9 μg m(-3) (average ± standard deviation), which is comparable to the concentration of organic aerosol but only 7.4 ± 1.2% of the concentration of speciated volatile organic compounds. Only 8.6 ± 2.2% of the mass of the primary IVOCs was speciated. Almost no weekend/weekday variation in the ambient concentration of both speciated and total primary IVOCs was observed, suggesting that petroleum-related sources other than on-road diesel vehicles contribute substantially to the IVOC emissions. Primary IVOCs are estimated to produce about 30% of newly formed SOA in the afternoon during CalNex, about 5 times that from single-ring aromatics. The importance of IVOCs in SOA formation is expected to be similar in many urban environments.

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Exploring the seasonal NMHC distribution in an urban area of the Middle East during ECOCEM campaigns: very high loadings dominated by local emissions and dynamics

Salameh

Sauvage²,

Afif

et al. 2015

Environ. Chem.

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Environmental context Non-methane hydrocarbons play an important role in the formation of photochemical oxidants such as ozone. We investigate factors controlling the distribution of non-methane hydrocarbons in an urban area of the Middle East. The study highlights the importance of local emissions and atmospheric dynamics, and the limited effect of photochemistry at the measurement site. Abstract Measurements of over 70 C2-C16 non-methane hydrocarbons (NMHCs) were conducted in suburban Beirut (1.3 million inhabitants) in summer 2011 and winter 2012 during the Emission and Chemistry of Organic Carbon in the East Mediterranean (ECOCEM) field campaign. The levels of NMHCs observed exceeded by a factor of two in total volume the levels found in northern mid-latitude megacities (Paris and Los Angeles), especially for the unburned fossil fuel fraction. Regardless of the season, the major compounds, explaining 50% of the concentrations, were toluene, isopentane, butane, m,p-xylenes, propane and ethylene, emitted by mobile traffic and gasoline evaporation sources. Most NMHCs show a distinct seasonal cycle, with a summer maximum and a winter minimum, unlike seasonal cycles usually observed in the northern mid-latitude urban areas. We show that NMHC distribution is mainly driven by strong local emissions and local atmospheric dynamics, with no clear evidence of photochemical removal in summer or influence from long-range transport.

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Volatile and intermediate-volatility organic compounds in sub-urban Paris: variability, origin and importance for SOA formation

Cited by 4 publications

References 160 publications

Radical budget analysis in a suburban European site during the MEGAPOLI summer field campaign

Radical budget analysis in a suburban European site during the MEGAPOLI summer field campaign

Intermediate-Volatility Organic Compounds: A Large Source of Secondary Organic Aerosol

Exploring the seasonal NMHC distribution in an urban area of the Middle East during ECOCEM campaigns: very high loadings dominated by local emissions and dynamics

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