Formation of peroxyacyl‐ and alkyl nitrates in irradiations of gasoline vapours under atmospheric conditions

Roumelis, Nikolaos; Glavas, Sotirios

doi:10.1080/09593339209385143

Cited by 7 publications

(3 citation statements)

References 14 publications

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“…The original GC/ECD technique [ Darley et al , 1963] has been improved through the use of capillary columns [ Roberts et al , 1989]. It can now provide measurements of PAN; PPN; MPAN; APAN (peroxyacryloyl nitrate, CH 2 CHC(O)OONO 2 ); and PiBN (peroxyisobutyryl nitrate, CH 3 CH(CH 3 )C(O)O 2 NO 2 ), a highly phytotoxic photooxidation product of gasoline vapor [e.g., Taylor , 1969; Roumelis and Glavas , 1992; Singh and Salas , 1983], every 5 min [ Williams et al , 2000; Roberts et al , 2001] with a detection limit of 5 pptv for PAN. A sampling rate of 1 min for PAN, PPN, and PiBN (but not MPAN) with a PAN detection limit of 10 pptv has been achieved by replacing the ECD with a luminol‐based detector [ Gaffney et al , 1999].…”

Section: Introductionmentioning

confidence: 99%

A thermal dissociation–chemical ionization mass spectrometry (TD‐CIMS) technique for the simultaneous measurement of peroxyacyl nitrates and dinitrogen pentoxide

2004

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[1] We have developed a thermal dissociation-chemical ionization mass spectrometry (TD-CIMS) technique for fast measurements of a series of peroxyacyl nitrates and dinitrogen pentoxide. Thermally generated acylperoxy radicals react with I À to produce a carboxylate ion that is unique for each parent species. NO 3 resulting from the decomposition of N 2 O 5 reacts with I À to form NO 3 À. The measurement technique was verified for PAN and PPN during an informal comparison with a gas chromatograph (GC) equipped with an electron capture detector (ECD) in Boulder, Colorado, during October 2002. Good agreement was obtained between the two instruments with R 2 = 0.91 for PAN (n = 657) and R 2 = 0.89 for PPN (n = 655). Detection limits of 7 pptv and 4 pptv were determined for PAN and PPN, respectively, for a 1 s integration period and a signal-to-noise ratio of 3. The TD-CIMS simultaneously detected ambient PiBN and N 2 O 5 + NO 3 in addition to PAN and PPN during the intercomparison period. We estimate a detection limit of 3 pptv in 1 s for PiBN. PnBN would be detected at the same mass, so we cannot rule out a contribution from PnBN to our PiBN estimate. Sensitivity to MPAN was found to be lower than to PAN in laboratory experiments, but a detection limit of 10 pptv can still be achieved by integrating for 15 s. Assuming the same sensitivity as for PAN, the detection limit for the sum of N 2 O 5 and NO 3 was estimated to be 12 pptv in 1 s. The fast time response of the TD-CIMS combined with a sensitivity and limit of detection comparable to the GC/ECD make this a promising technique for PAN flux measurements by eddy covariance. PAN uptake by different types of vegetation could be important input for global and regional ozone models, and PAN deposition to snow is of interest in polar regions.

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Section: Introductionmentioning

confidence: 99%

A thermal dissociation–chemical ionization mass spectrometry (TD‐CIMS) technique for the simultaneous measurement of peroxyacyl nitrates and dinitrogen pentoxide

2004

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“…The important reactions occurring in indoor environment are (i) O 3 reacts with unsaturated hydrocarbons, (ii) production of •OH radicals by the reaction of O 3 and NOx, (iii) decomposition of PAN (peroxyacetyl-nitrate), (iv) free radical reaction with VOCs, and (v) other heterogeneous reactions [11,[15][16][17]. Note that the reactions in the indoor environment mentioned above are thermodynamically favourable.…”

Section: Reactive Chemistrymentioning

confidence: 99%

Chemistry of Indoor Pollutants and Their Impacts on Human Health

Davamani

Deepasri

Parameswari

et al. 2020

IRJPAC

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Indoor air pollution refers to the deterioration of indoor air quality by harmful chemicals and other products, which can be up to 10 times worse than the outdoor air pollution. Almost 90% of the modern human time is spent indoors. In India, out of 0.2 billion people using fuel for cooking; 49% use ﬁrewood; 8.9% cow dung cake; 1.5% coal, lignite, or charcoal; 2.9% kerosene; 28.6% liqueﬁed petroleum gas (LPG); 0.1% electricity; 0.4% biogas; and 0.5% any other means. The negative consequences of indoor air pollution result in around 2 million premature deaths every year, with 44% are due to pneumonia, 54% from chronic obstructive pulmonary disease (COPD), and 2% from lung cancer. The so-called "natural" or "ecologic" goods are not inherently free of adverse health effects. Certain other constituents such as terpenoids and linseed oil may be chemically reactive than those from non-ecologic products. Secondary emissions from these products may present a greater risk to human health than those compounds which are substitutes for their precursors.

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“…In contrast, MPAN is derived primarily from the photo-oxidation of biogenic hydrocarbons, particularly isoprene (Tuazon and Atkinson, 1990;Bertman and Roberts, 1991). Other APNs have also been recently detected in the field, including APAN (Roberts et al, 2001;Tanimoto and Akimoto, 2001), PnBN (Grosjean et al, 1993;Glavas and Moschonas, 2001) and PiBN (Roberts et al, 2002(Roberts et al, , 2003, all phytotoxic compounds associated with petrochemical precursors (Taylor, 1969;Roumelis and Glavas, 1992). Speciation of APNs can provide insight into sources of photochemical ozone precursors, especially near urban regions where recent photochemical production yields high APN concentrations (Williams et al, 1997;Roberts et al, 1998Roberts et al, , 2002.…”

Section: Correlations Among Apnsmentioning

confidence: 99%

Influence of trans-Pacific pollution transport on acyl peroxy nitrate abundances and speciation at Mount Bachelor Observatory during INTEX-B

Wolfe¹,

McNeill²,

Jaffe³

et al. 2007

Preprint

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Abstract. We present month-long observations of speciated acyl peroxy nitrates (APNs), including PAN, PPN, MPAN, APAN, and the sum of PiBN and PnBN, measured at the Mount Bachelor Observatory (MBO) as part of the INTEX-B collaborative field campaign during spring 2006. APN abundances, measured by thermal dissociation-chemical ionization mass spectrometry (TD-CIMS), are discussed in terms of differing contributions from the boundary layer and the free troposphere and in the context of previous APN measurements in the NE Pacific region. PAN mixing ratios range from 11 to 3955 pptv, with a mean value of 334 pptv for the full measurement period. PPN is linearly correlated with PAN (r2=0.96), with an average abundance of 6.5% relative to PAN; other APNs are generally <1% of PAN. Diurnal cycles and relationships of APNs with ozone reveal a gradient in hydrocarbon chemistry between the boundary layer and the free troposphere. On average, the highest levels of APNs, ozone and PPN/PAN are found in free tropospheric air masses, suggesting that this site is strongly influenced by distant pollution sources. To estimate the impact of long-range transport of Asian pollution on atmospheric composition at MBO, we perform a detailed analysis utilizing HYSPLIT back trajectories. This analysis suggests that trans-Pacific transport of Asian pollution leads to substantial increases in APN and ozone mixing ratios at MBO, especially when transport occurs via the free troposphere. The ensemble of trajectories indicate that Asian-influenced free tropospheric air was sampled in ~16% of our data and contained a median PAN mixing ratio double that of the full dataset.

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Formation of peroxyacyl‐ and alkyl nitrates in irradiations of gasoline vapours under atmospheric conditions

Cited by 7 publications

References 14 publications

A thermal dissociation–chemical ionization mass spectrometry (TD‐CIMS) technique for the simultaneous measurement of peroxyacyl nitrates and dinitrogen pentoxide

A thermal dissociation–chemical ionization mass spectrometry (TD‐CIMS) technique for the simultaneous measurement of peroxyacyl nitrates and dinitrogen pentoxide

Chemistry of Indoor Pollutants and Their Impacts on Human Health

Influence of trans-Pacific pollution transport on acyl peroxy nitrate abundances and speciation at Mount Bachelor Observatory during INTEX-B

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