Measurement of Volatile Organic Compounds in Vehicle Exhaust Using Single-Photon Ionization Time-of-Flight Mass Spectrometry

Yamamoto, Yukio; Kambe, Yasuaki; Yamada, Hiroyuki; Tonokura, Kenichi

doi:10.2116/analsci.28.385

Cited by 19 publications

(10 citation statements)

References 26 publications

(43 reference statements)

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“…Normalised reactivity R (gO 3 /gNMHCs emitted) is generally used to indicate OFP for NMHCs from emission sources using their source profiles and maximum incremental reactivity (MIR) values, using Eq. (3) as follows (Harley et al, 2000;Zhang et al, 2013):…”

Section: Compounds Precision Precision Lod Uncertainty Compounds Precmentioning

confidence: 99%

“…The ratio of two NMHCs with different chemical lifetimes can also be used to constrain the photochemical age of air masses and atmospheric transport times (Parrish et al, 1992;McKeen and Liu, 1993). Several source profiles have been compiled for different emission sources in North America Gentner et al, 2012), Europe (Passant, 2002;Niedojadlo et al, 2007), East Asia (Na et al, 2004;Liu et al, 2008;Zhang et al, 2013;Zheng et al, 2013;Mo et al, 2016;Hong-li et al, 2017) and other areas (Doskey et al, 1999); however, there is still a considerable gap in the data of speciated NMHCs from active emission sources in South Asia. Using the emission source profiles from different regions of the world for modelling and emission inventories can result in large uncertainties as the emissions can change from country to country, depending upon the quality and composition of fuels, combustion practices and vehicular fleet.…”

Section: Introductionmentioning

confidence: 99%

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Non-methane hydrocarbon (NMHC) fingerprints of major urban and agricultural emission sources for use in source apportionment studies

et al. 2020

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Abstract. In complex atmospheric emission environments such as urban agglomerates, multiple sources control the ambient chemical composition driving air quality and regional climate. In contrast to pristine sites, where reliance on single or a few chemical tracers is often adequate for resolving pollution plumes and source influences, the comprehensive chemical fingerprinting of sources using non-methane hydrocarbons (NMHCs) and the identification of suitable tracer molecules and emission ratios becomes necessary. Here, we characterise and present chemical fingerprints of some major urban and agricultural emission sources active in South Asia, such as paddy stubble burning, garbage burning, idling vehicular exhaust and evaporative fuel emissions. A total of 121 whole air samples were actively collected from the different emission sources in passivated air sampling steel canisters and then analysed for 49 NMHCs (22 alkanes, 16 aromatics, 10 alkenes and one alkyne) using thermal desorption gas chromatography flame ionisation detection. Several new insights were obtained. Propane was found to be present in paddy stubble fire emissions (8 %), and therefore, for an environment impacted by crop residue fires, the use of propane as a fugitive liquefied petroleum gas (LPG) emission tracer must be done with caution. Propene was found to be ∼ 1.6 times greater (by weight) than ethene in smouldering paddy fires. Compositional differences were observed between evaporative emissions of domestic LPG and commercial LPG, which are used in South Asia. While the domestic LPG vapours had more propane (40 ± 6 %) than n-butane (19 ± 2 %), the converse was true for commercial LPG vapours (7 ± 6 % and 37 ± 4 %, respectively). Isoprene was identified as a new tracer for distinguishing paddy stubble and garbage burning in the absence of isoprene emissions at night from biogenic sources. Analyses of source-specific inter-NMHC molar ratios revealed that toluene/benzene ratios can be used to distinguish among paddy stubble fire emissions in the flaming (0.38 ± 0.11) and smouldering stages (1.40 ± 0.10), garbage burning flaming (0.26 ± 0.07) and smouldering emissions (0.59 ± 0.16), and traffic emissions (3.54 ± 0.21), whereas i-pentane ∕ n-pentane can be used to distinguish biomass burning emissions (0.06–1.46) from the petrol-dominated traffic and fossil fuel emissions (2.83–4.13). i-butane ∕ n-butane ratios were similar (0.20–0.30) for many sources and could be used as a tracer for photochemical ageing. In agreement with previous studies, i-pentane, propane and acetylene were identified as suitable chemical tracers for petrol vehicular and evaporative emissions, LPG evaporative and vehicular emissions and flaming-stage biomass fires, respectively. The secondary pollutant formation potential and human health impact of the sources was also assessed in terms of their hydroxyl radical (OH) reactivity (s−1), ozone formation potential (OFP; gO3/gNMHC) and fractional benzene, toluene, ethylbenzene and xylenes (BTEX) content. Petrol vehicular emissions, paddy stubble fires and garbage fires were found to have a higher pollution potential (at ≥95 % confidence interval) relative to the other sources studied in this work. Thus, many results of this study provide a new foundational framework for quantitative source apportionment studies in complex emission environments.

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Section: Compounds Precision Precision Lod Uncertainty Compounds Precmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Non-methane hydrocarbon (NMHC) fingerprints of major urban and agricultural emission sources for use in source apportionment studies

et al. 2020

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“…SOA is ubiquitous and dominates the total OA in various atmospheric environments, accounting for approximately two-thirds of the total OA in urban areas to almost 90 % in urban downwind and rural areas in Northern Hemisphere midlatitudes (Zhang et al, 2007). China, for example, has serious air quality problems due to PM 2.5 pollution in the recent decades (Chan and Yao, 2008; and SOA contributed 30-90 % of OA mass in its megacities (He et al, 2001;Cao et al, 2003;Duan et al, 2005Duan et al, , 2007Yang et al, 2005;Hagler et al, 2006). However, models generally underestimate the observed OA levels mainly due to the unclear sources and formation processes of SOA (de Gouw et al, 2005;Heald et al, 2005;Johnson et al, 2006;Volkamer et al, 2006).…”

Section: Introductionmentioning

confidence: 99%

Secondary organic aerosol formation from photochemical aging of light-duty gasoline vehicle exhausts in a smog chamber

et al. 2015

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Abstract. In China, a rapid increase in passenger vehicles has led to the growing concern of vehicle exhaust as an important source of anthropogenic secondary organic aerosol (SOA) in megacities hard hit by haze. In this study, the SOA formation of emissions from two idling light-duty gasoline vehicles (LDGVs) (Euro 1 and Euro 4) operated in China was investigated in a 30 m3 smog chamber. Five photo-oxidation experiments were carried out at 25 °C with relative humidity at around 50 %. After aging at an OH exposure of 5 × 106 molecules cm−3 h, the formed SOA was 12–259 times as high as primary organic aerosol (POA). The SOA production factors (PF) were 0.001–0.044 g kg−1 fuel, comparable with those from the previous studies at comparable OH exposure. This quite lower OH exposure than that in typical atmospheric conditions might however lead to the underestimation of the SOA formation potential from LDGVs. Effective SOA yields in this study were well fit by a one-product gas-particle partitioning model but quite lower than those of a previous study investigating SOA formation from three idling passenger vehicles (Euro 2–4). Traditional single-ring aromatic precursors and naphthalene could explain 51–90 % of the formed SOA. Unspeciated species such as branched and cyclic alkanes might be the possible precursors for the unexplained SOA. A high-resolution time-of-flight aerosol mass spectrometer was used to characterize the chemical composition of SOA. The relationship between f43 (ratio of m/z 43, mostly C2H3O+, to the total signal in mass spectrum) and f44 (mostly CO2+) of the gasoline vehicle exhaust SOA is similar to the ambient semi-volatile oxygenated organic aerosol (SV-OOA). We plot the O : C and H : C molar ratios of SOA in a Van Krevelen diagram. The slopes of ΔH : C / ΔO : C ranged from −0.59 to −0.36, suggesting that the oxidation chemistry in these experiments was a combination of carboxylic acid and alcohol/peroxide formation.

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“…Single photon ionization (SPI) is another attractive soft ionization technique because of its low degree of fragmentation with simple spectrum interpretation compared with conventional EI method [26,27], especially for complex samples (e.g., gasoline and diesel [28,29], cigarette smoke [30], and volatile organic compounds (VOCs) [31][32][33]). The coupling of SPI with time-of-flight mass spectrometer (SPI-TOFMS) has the advantages of both rapid detection speed and simple spectra analysis [34,35].…”

Section: Introductionmentioning

confidence: 99%

Rapid Identification and Quantification of Linear Olefin Isomers by Online Ozonolysis-Single Photon Ionization Time-of-Flight Mass Spectrometry

Xie

Chen

Lee

et al. 2015

J. Am. Soc. Mass Spectrom.

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Abstract. The specific locations of the double bonds in linear olefins can facilitate olefin catalytic synthetic reactions to improve the quality of target olefin products. We developed a simple and efficient approach based on single photon ionization time-offlight mass spectrometry (SPI-TOFMS) combined with online ozonolysis to identify and quantify the linear olefin double bond positional isomers. The online ozonolysis cleaved the olefins at the double bond positions that led to formation of corresponding characteristic aldehydes. The aldehydes were then detected by SPI-TOFMS to achieve unique spectrometric Bfingerprints^for each linear olefin to successfully identify the isomeric ones. To accurately quantify the isomeric components in olefin mixtures, an algorithm was proposed to quantify three isomeric olefin mixtures based on characteristic ion intensities and their equivalent ionization coefficients. The relative concentration errors for the olefin components were lower than 2.5% while the total analysis time was less than 2 min. These results demonstrate that the online ozonolysis SPI-TOFMS has the potential for real-time monitoring of catalytic olefin synthetic reactions.

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Measurement of Volatile Organic Compounds in Vehicle Exhaust Using Single-Photon Ionization Time-of-Flight Mass Spectrometry

Abstract: We applied a compact, laser-based VUV-SPI-TOFMS for the real-time measurement of VOCs in exhaust with high sensitivity.

Cited by 19 publications

References 26 publications

Non-methane hydrocarbon (NMHC) fingerprints of major urban and agricultural emission sources for use in source apportionment studies

Non-methane hydrocarbon (NMHC) fingerprints of major urban and agricultural emission sources for use in source apportionment studies

Secondary organic aerosol formation from photochemical aging of light-duty gasoline vehicle exhausts in a smog chamber

Rapid Identification and Quantification of Linear Olefin Isomers by Online Ozonolysis-Single Photon Ionization Time-of-Flight Mass Spectrometry

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