Thermal Lifetimes of Peroxynitrates Occurring in the Atmospheric Degradation of Oxygenated Fuel Additives

Kirchner, F.; Thüner, Lars P.; Barnes, Ian; Becker, Karl‐Heinz; Donner, B.; Zabel, F.

doi:10.1021/es9609415

Cited by 36 publications

(36 citation statements)

References 18 publications

(25 reference statements)

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“…2.2.3. After the UV lamp is turned off, the ratio between PAN and PANs inside the chamber is fixed since the thermal lifetimes of both species are very similar (Kirchner et al, 1997(Kirchner et al, , 1999 and wall losses are negligible. This ratio was determined by FTIR and checked during the course of the experiment, and the stability of the mixing ratios inside the chamber was confirmed.…”

Section: Dissociation Temperaturementioning

confidence: 99%

“…(Tyndall et al, 2004;Wallington et al, 2001;Kirchner et al, 1997). Methyl formate is used primarily in the chemical industry to manufacture formamide, dimethylformamide and formic acid.…”

Section: Mass 75mentioning

confidence: 99%

“…Removal processes of PAN compounds from the atmosphere are primarily photolysis in the upper troposphere and thermal decomposition in the lower troposphere, with minor contributions from chemical reactions with OH or Cl radicals (Talukdar et al, 1995). The thermal decomposition rate is highly temperature dependent, with lifetimes ranging from about 30 minutes at 298 K to 8 h at 273 K. At temperatures characteristic of the middle and upper troposphere, the lifetime of PAN can be on the order of months (Kirchner et al, 1999;Kirchner et al, 1997). This makes PAN and some of its homologues important reservoirs of NO x (NO and NO 2 ) and a significant, and often dominant, fraction of reactive nitrogen throughout much of the remote troposphere (Singh and Hanst, 1981).…”

Section: Introductionmentioning

confidence: 99%

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Characterization of a thermal decomposition chemical ionization mass spectrometer for the measurement of peroxy acyl nitrates (PANs) in the atmosphere

et al. 2011

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Abstract. This paper presents a detailed laboratory characterization of a thermal dissociation chemical ionization mass spectrometer (TD-CIMS) for the atmospheric measurement of Peroxyacetyl nitrate (PAN) and its homologues (PANs). PANs are efficiently dissociated in a heated inlet and the resulting peroxy acyl radicals are reacted with I − ions in a flow tube. The mass spectrometer detects the corresponding carboxylate ions. PAN, peroxypropionyl nitrate (PPN), peroxyisobutyryl nitrate (PiBN), peroxy-n-butyryl nitrate (PnBN), peroxyacryloyl nitrate (APAN), peroxycrotonyl nitrates (CPAN) and peroxymethacryloyl nitrate (MPAN) were cross-calibrated with both a dual channel GC/ECD and a total odd-nitrogen (NO y ) instrument for the NCAR TD-CIMS' typical aircraft operation conditions. In addition, the instrument sensitivity to a number of more exotic PANs (peroxyhydroxyacetyl nitrate, methoxyformyl peroxynitrate, and peroxybenzoyl nitrate) was evaluated qualitatively by comparisons with a long-path FTIR instrument.The sensitivity for PPN is slightly higher than that of PAN. Larger aliphatic and olefinic PAN compounds generally showed lower sensitivities. We postulate that these differences are owing to secondary reactions in the thermal decomposition region, which either reduce the yield of peroxy acyl radicals or cause losses of these radicals through intramolecular decomposition. The relative importance of these secondary reactions varies considerably between different PAN species.Correspondence to: F. M. Flocke (ffl@ucar.edu)Results also indicate that the reaction of the larger peroxy acyl radicals with the ion-water cluster, I − (H 2 O)n proceeds about an order of magnitude faster than with I − alone, as has been observed for peroxy acetyl radicals. Sensitivity variations among the individual PAN species at very low water vapor were observed. The results call for careful evaluation of each PAN species to be measured and for each desired operating condition of a TD-CIMS instrument.

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Section: Dissociation Temperaturementioning

confidence: 99%

“…(Tyndall et al, 2004;Wallington et al, 2001;Kirchner et al, 1997). Methyl formate is used primarily in the chemical industry to manufacture formamide, dimethylformamide and formic acid.…”

Section: Mass 75mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Characterization of a thermal decomposition chemical ionization mass spectrometer for the measurement of peroxy acyl nitrates (PANs) in the atmosphere

et al. 2011

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“…Vehicle exhaust emissions data have shown that acetaldehyde emissions can increase by as much as 100% with the use of 2.0 wt % ethanol oxygenated gasoline, part of which undergoes photochemical reactions in the atmosphere to make peroxyacetyl nitrate (PAN) (17). Reuter et al (4) reported that benzene emissions are reduced by fuel oxygenate.…”

Section: Figure 3 Effect Of Ethanol Concentration and Vehicles' Emismentioning

confidence: 99%

Environmental Implications on the Oxygenation of Gasoline with Ethanol in the Metropolitan Area of Mexico City

Schifter

Vera

Díaz

et al. 2001

Environ. Sci. Technol.

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Motor vehicle emission tests were performed on 12 inuse light duty vehicles, made up of the most representative emission control technologies in Mexico City: no catalyst, oxidative catalyst, and three way catalyst. Exhaust regulated (CO, NO x , and hydrocarbons) and toxic (benzene, formaldehyde, acetaldehyde, and 1,3-butadiene) emissions were evaluated for MTBE (5 vol %)-and ethanol (3, 6, and 10 vol %)-gasoline blends. The most significant overall emissions variations derived from the use of 6 vol % ethanol (relative to a 5% MTBE base gasoline) were 16% decrease in CO, 28% reduction in formaldehyde, and 80% increase in acetaldehyde emissions. A 26% reduction in CO emissions from the oldest fleet (

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“…XO 2 accounts for additional NO to NO 2 conversions, MO 2 represents methyl peroxy radical and ACO 3 regroups all the acetyl peroxy and higher saturated acyl peroxy radicals. Further details can be found in Atkinson (1994), Kirchner et al (1997) and V2003.…”

Section: Numerical Setupmentioning

confidence: 99%

Impacts of using reformulated and oxygenated fuel blends on the regional air quality of the upper Rhine valley

2006

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Abstract. The effects of using three alternative gasoline fuel blends on regional air quality of the upper Rhine valley have been investigated. The first of the tested fuels is oxygenated by addition of ethyl-tertio-butyl ether (ETBE), the second is based on a reformulation of its composition and the third on is both oxygenated and reformulated. The upper Rhine valley is a very sensitive region for pollution episodes and several meteorological and air quality studies have already been performed. High temporal and spatial emission inventories are available allowing relevant and realistic modifications of the emission inventories. The calculation period, i.e., 11 May 1998, corresponds to a regional photochemical ozone pollution episode during which ozone concentrations exceeded several times the information threshold of the ozone directive of the European Union (180 µg m −3 as 1 hourly average). New emission inventories are set up using specific emission factors related to the alternative fuels by varying the fraction of gasoline passenger cars (from 50% to 100%) using the three fuel blends. Then air quality modeling simulations are performed using these emission inventories over the upper Rhine valley. The impact of alternative fuels on regional air quality is evaluated by comparing these simulations with the one using a reference emission inventory, e.g., where no modifications of the fuel composition are included. The results are analyzed by focusing on peak levels and daily averaged concentrations. The use of the alternative fuels leads to general reductions of ozone and volatile organic compounds (VOC) and increases of NO x levels. We found different behaviors related to the type of the area of concern i.e. rural or urban. The impacts on ozone are enhanced in urban areas where 15% reduction of the ozone peak and daily averaged concentrations can be reached. This behavior is similar for the NO x for which, in addition, an increase of the levels canCorrespondence to: J.-L. Ponche (ponche@illite.u-strasbg.fr) be noted in urban plumes over rural areas. The most important decreases of the total VOC levels are mainly located over rural areas (more than 5% reduction of the levels except in urban plumes). By comparing these results with those from a local study related to the air quality of Strasbourg, we estimate that the regional contribution to the urban air quality of Strasbourg allows an enhancement of the results by using alternative fuel blends at the regional scale.

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Thermal Lifetimes of Peroxynitrates Occurring in the Atmospheric Degradation of Oxygenated Fuel Additives

Cited by 36 publications

References 18 publications

Characterization of a thermal decomposition chemical ionization mass spectrometer for the measurement of peroxy acyl nitrates (PANs) in the atmosphere

Characterization of a thermal decomposition chemical ionization mass spectrometer for the measurement of peroxy acyl nitrates (PANs) in the atmosphere

Environmental Implications on the Oxygenation of Gasoline with Ethanol in the Metropolitan Area of Mexico City

Impacts of using reformulated and oxygenated fuel blends on the regional air quality of the upper Rhine valley

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