Stable carbon isotope composition of nonmethane hydrocarbons in emissions from transportation related sources and atmospheric observations in an urban atmosphere

Rudolph, J.; Czuba, E.; Norman, Ann‐Lise; Huang, Lin; Ernst, D.

doi:10.1016/s1352-2310(01)00537-4

Cited by 97 publications

(119 citation statements)

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“…Irei et al (2015) reported that the main factor determining the carbon isotope ratio of the particulate phase products of toluene oxidation is the kinetic isotope effect (KIE) for the reaction of toluene with the OH radical and the carbon isotope ratio of the reacting toluene. The KIEs for the reactions of benzene, toluene and m-xylene with the OH radical have been measured in the laboratory (Anderson et al, 2004) and the carbon isotope ratio of their emissions in the Greater Toronto Area (GTA) have been determined by Rudolph et al (2002). Using these values, which are summarized in Ta- Table 3.…”

Section: Overview Of Measured Carbon Isotope Ratiosmentioning

confidence: 99%

“…The first reason is that nitrophenols are formed from one reaction pathway and are specific to the aromatic VOC + OH reaction (Forstner et al, 1997). This is important so that the nitrophenols can be traced back to the precursor, which has a measured and known isotope ratio at the source (Rudolph et al, 2002). Secondly, the target compounds should be ring retaining products so that the possibility of being formed from other precursors decreases compared to ring fragmentation products.…”

Section: Introductionmentioning

confidence: 99%

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Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

et al. 2015

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Abstract.A method to quantify concentrations and stable carbon isotope ratios of secondary organic aerosols has been applied to study atmospheric nitrophenols in Toronto, Canada. The sampling of five nitrophenols, all with substantial secondary formation from the photooxidation of aromatic volatile organic compounds (VOCs), was conducted in the gas phase and particulate matter (PM) together and in PM alone. Their concentrations in the atmosphere are in the low ng m −3 range and, consequently, a large volume of air (> 1000 m 3 ) is needed to analyze samples for stable carbon isotope ratios, resulting in sampling periods of typically 24 h. While this extended sampling period increases the representativeness of average values, it at the same time reduces possibilities to identify meteorological conditions or atmospheric pollution levels determining nitrophenol concentrations and isotope ratios.Average measured carbon isotope ratios of the different nitrophenols are between −34 and −33 ‰, which is well within the range predicted by mass balance. However, the observed carbon isotope ratios cover a range of nearly 9 ‰ and approximately 20 % of the isotope ratios of the products have isotope ratios lower than predicted from the kinetic isotope effect of the first step of the reaction mechanism and the isotope ratio of the precursor. This can be explained by isotope fractionation during reaction steps following the initial reaction of the precursor VOCs with the OH radical.Limited evidence for local production of nitrophenols is observed since sampling was done in the Toronto area, an urban center with significant anthropogenic emission sources. Strong evidence for significant local formation of nitrophenols is only found for samples collected in summer. On average, the difference in carbon isotope ratios between nitrophenols in the particle phase and in the gas phase is insignificant, but for a limited number of observations in summer, a substantial difference is observed. This indicates that at high OH radical concentrations, photochemical formation or removal of nitrophenols can be faster than exchange between the two phases.The dependence between the concentrations and isotope ratios of the nitrophenols and meteorological conditions as well as pollution levels (NO 2 , O 3 , SO 2 and CO) demonstrate that the influence of precursor concentrations on nitrophenol concentrations is far more important than the extent of photochemical processing. While it cannot be excluded that primary emissions contribute to the observed levels of nitrophenols, overall the available evidence demonstrates that secondary formation is the dominant source for atmospheric nitrophenols in Toronto.

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Section: Overview Of Measured Carbon Isotope Ratiosmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

et al. 2015

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“…The small difference in carbon isotopic abundance between the two seasons in Hong Kong is consistent with similar source mixtures. Rudolph et al (2002) also observed little variability in 13 C abundances for nonmethane hydrocarbons (NMHC) from traffic-related sources in the metropolitan region of Toronto. As shown in Fig.…”

Section: Stable Carbon Isotopic Composition Of Oc and Ecmentioning

confidence: 99%

Variability of organic and elemental carbon, water soluble organic carbon, and isotopes in Hong Kong

et al. 2006

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Abstract.To determine the levels and variations of carbonaceous aerosol in Hong Kong, PM 2.5 and PM 10 samples were collected by high volume (Hi-vol) samplers at three monitoring stations (representing middle-scale roadside, urban-, and regional-scale environments) during winter (November 2000 to February 2001) and summer (June 2001 to August 2001) periods. The highest concentrations of organic carbon (OC), elemental carbon (EC), and water-soluble organic carbon (WSOC) were found at the middle-scale roadside site with the lowest at the regional-scale site. The percentages of WSOC in total carbon at these sites were inversely correlated with their concentrations (i.e., the highest percentages of WSOC were observed at the regional-scale site). A high WSOC fraction may be associated with aged aerosol because of the secondary formation by photochemical oxidation of organic precursors of anthropogenic pollutants during transport. The annual average of isotope abundances (δ 13 C) of OC and EC were -26.9±0.5‰ and -25.6±0.1‰, respectively. There were no notable differences for seasonal distributions of carbon isotopic composition, consistent with motor vehicle emissions being the main source contributors of carbonaceous aerosol in Hong Kong. OC 13 C abundances at the regional-scale site were higher than those at the middle-scale roadside and urban sites, consistent with secondary organic aerosols of biogenic origin.

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“…Statistically insignificant variability in emission isotope ratios for transportation-related sources of selected NMHCs has been reported by Rudolph et al (2002) with the signatures for the majority of species equating to within the measurement precision of 2 ‰ that of CO mentioned above. The exception of significant enrichment was found for ethyne (C 2 H 2 ), which is not represented in the MECCA chemistry mechanism (as of EVAL 2 set-up) and may potentially constitute an enriched but very moderate source (see, for example, Ho et al, 2009).…”

Section: For Details)mentioning

confidence: 80%

Uncertainties of fluxes and <sup>13</sup>C  ∕ <sup>12</sup>C ratios of atmospheric reactive-gas emissions

2017

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Abstract. We provide a comprehensive review of the proxy data on the 13 C / 12 C ratios and uncertainties of emissions of reactive carbonaceous compounds into the atmosphere, with a focus on CO sources. Based on an evaluated set-up of the EMAC model, we derive the isotope-resolved data set of its emission inventory for the 1997-2005 period. Additionally, we revisit the calculus required for the correct derivation of uncertainties associated with isotope ratios of emission fluxes. The resulting δ 13 C of overall surface CO emission in 2000 of −(25.2 ± 0.7) ‰ is in line with previous bottom-up estimates and is less uncertain by a factor of 2. In contrast to this, we find that uncertainties of the respective inverse modelling estimates may be substantially larger due to the correlated nature of their derivation. We reckon the δ 13 C values of surface emissions of higher hydrocarbons to be within −24 to −27 ‰ (uncertainty typically below ±1 ‰), with an exception of isoprene and methanol emissions being close to −30 and −60 ‰, respectively. The isotope signature of ethane surface emission coincides with earlier estimates, but integrates very different source inputs. δ 13 C values are reported relative to V-PDB.

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Stable carbon isotope composition of nonmethane hydrocarbons in emissions from transportation related sources and atmospheric observations in an urban atmosphere

Cited by 97 publications

References 11 publications

Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

Variability of organic and elemental carbon, water soluble organic carbon, and isotopes in Hong Kong

Uncertainties of fluxes and <sup>13</sup>C  ∕ <sup>12</sup>C ratios of atmospheric reactive-gas emissions

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Stable carbon isotope composition of nonmethane hydrocarbons in emissions from transportation related sources and atmospheric observations in an urban atmosphere

Cited by 97 publications

References 11 publications

Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

Variability of organic and elemental carbon, water soluble organic carbon, and isotopes in Hong Kong

Uncertainties of fluxes and &lt;sup&gt;13&lt;/sup&gt;C ∕ &lt;sup&gt;12&lt;/sup&gt;C ratios of atmospheric reactive-gas emissions

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Uncertainties of fluxes and <sup>13</sup>C  ∕ <sup>12</sup>C ratios of atmospheric reactive-gas emissions