Atmospheric chemistry of isoprene and of its carbonyl products

Grosjean, Daniel; Williams, Edwin L.; Grosjean, Eric

doi:10.1021/es00042a004

Cited by 218 publications

(203 citation statements)

References 27 publications

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“…In the case of the unsymmetric diene, isoprene (the only such compound currently considered in the MCM), addition of ozone to the less substituted double bond is assumed to be favoured relative to the more substituted double bond by a factor of 1.5, which is in accordance with the results of Grosjean et al (1993) and Aschmann and Atkinson (1994).…”

Section: Initial Productssupporting

confidence: 71%

“…This arises because the mechanism of the OHinitiated chemistry is NO X -dependent, and also because the ozone-initiated chemistry makes a contribution at the low end of the NO X range, when the simulated levels of OH are substantially lower. It is well established that the yield ratio of the primary products MACR/MVK is greater from the ozone initiated chemistry than from the OH-initiated chemistry (Grosjean et al, 1993;Aschmann and Atkinson, 1994), and also that the MACR/MVK ratio increases at low NO X during OH-initiated oxidation Ruppert and Becker, 2000). Because MPAN is derived exclusively from MACR, this has a particular influence on the simulated PAN/MPAN ratio, which was found to vary from 7.8 at the low end of the NO X range to 11.8 close to the high end of the range.…”

Section: Resultsmentioning

confidence: 99%

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Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

et al. 2003

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Abstract. Kinetic and mechanistic data relevant to the tropospheric degradation of volatile organic compounds (VOC), and the production of secondary pollutants, have previously been used to define a protocol which underpinned the construction of a near-explicit Master Chemical Mechanism. In this paper, an update to the previous protocol is presented, which has been used to define degradation schemes for 107 non-aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). The treatment of 18 aromatic VOC is described in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the reactions of the radical intermediates and the further degradation of first and subsequent generation products. Emphasis is placed on updating the previous information, and outlining the methodology which is specifically applicable to VOC not considered previously (e.g., α-and β-pinene). The present protocol aims to take into consideration work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Application of MCM v3 in appropriate box models indicates that the representation of isoprene degradation provides a good description of the speciated distribution of oxygenated organic products observed in reported field studies where isoprene was the dominant emitted hydrocarbon, and that the α-pinene degradation chemistry provides a good description of the time dependence of key gas phase species in α-pinene/NO X photo-oxidation experiments carried out in the European Photoreactor (EU-PHORE). Photochemical Ozone Creation Potentials (POCP) have been calculated for the 106 non-aromatic non-methane VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. Where applicable, the values are compared with those calculated with previous versions of the MCM.

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Section: Initial Productssupporting

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

et al. 2003

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“…The average k RR value for MACR, (1.9 ± 0.12) × 10 -18 cm 3 molecule -1 s -1 , is about 50-75% higher than the four rate constants for this reaction reported by Grosjean et al (1993) [(1.02 ± 0.05) × 10 -18 ], Grosjean and Grosjean (1998) [(1.08 ± 0.21) × 10 -18 ], Atkinson et al (1981) [(1.12 ± 0.13) × 10 -18 ], and Neeb et al (1998) [(1.30 ± 0.14) × 10 -18 ], all in units of cm 3 molecule -1 s -1 . That our experimental rate constant for MACR is higher than other reported values, with rate constants for all other VOCs in agreement with literature, suggests that there are additional processes removing MACR.…”

Section: Wall Loss and Relative Rate Experimentscontrasting

confidence: 52%

The stable-carbon kinetic isotope effects of the reactions of isoprene, methacrolein, and methyl vinyl ketone with ozone in the gas phase

Iannone¹,

Koppmann²,

Rudolph³

2008

Atmospheric Environment

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The stable-carbon kinetic isotope effects (KIEs) for the gas-phase reactions of isoprene, methacrolein (MACR), and methyl vinyl ketone (MVK) with ozone were studied in a 25 L reaction chamber at (298 ± 2) K and ambient pressure. The time dependence of both the stable-carbon isotope ratios and the concentrations was determined using a gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) system. The volatile organic compounds (VOCs) used in the KIE experiments had natural-abundance isotopic composition thus KIE data obtained from these experiments can be directly applied to atmospheric studies of isoprene chemistry.

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“…Isoprene was treated as a regular alkene species in Carter (1990) and lumped into an alkene group in COND2243. Its explicit reactions, excluding ISOP + N0 3 , and the reactions involving MACR and MVK were derived in the present work from more recent experimental results (Paulson et al, 1992a,b;Paulson and Seinfeld, 1992;Aschmann and Atkinson, 1994;Grosjean et al, 1993;Atkinson, 1990, 1989). Since there is no new experimental evidence to support a new reaction scheme for the ISOP + N0 3 reaction, the reaction used in Carter (1990) was adopted.…”

Section: Modification Of the Cond2243 Mechanismmentioning

confidence: 99%

Sensitivity of ozone concentrations to rate constants in a modified SAPRC90 chemical mechanism used for Canadian lower Fraser Valley ozone studies

Jiang

Singleton

McLaren

et al. 1997

Atmospheric Environment

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Abstract-The SAPRC90 chemical mechanism implemented in CALGRID is modified and updated for the specific emiSi;ions and applications ofthe Lower Fraser Valley (LFV) of British Columbia, Canada. Explicit reactions rehlted to biogenic emissions and alternative fuels are added. The sensitivity ofozone formation to rate parameters in the mechanism is determined for an episode specific trajectory which originates under relatively clean marine conditions and passes over the urban core of Vancouver during the morning rush hour. Of the 137 reactions in the modified mechanism. the rate constants of 44 reactions are found to have a high sensitivity on ozone formation. The 44 reactions are further divided into general sensitive reactions, for which rate constant changes near the base case values have observable effects on maximum ozone concentrations. and limit-sensitive reactions, for which rate constant changes of more than an order of magnitude are required to have an observable impact on ozone concentrations. For the sensitive reactions, both ozone sensitivity coefficients for small changes (20%) in the rate constants and effects on ozone caused by large rate constant changes (factors of 0, 0.5, and 2) are calculated. Of note is the importance of several photolysis reactions and the reactions ofOH with a class of reactive aromatics, including xylenes, on ozone concentrations in the LFV. Crown

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Atmospheric chemistry of isoprene and of its carbonyl products

Cited by 218 publications

References 27 publications

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

The stable-carbon kinetic isotope effects of the reactions of isoprene, methacrolein, and methyl vinyl ketone with ozone in the gas phase

Sensitivity of ozone concentrations to rate constants in a modified SAPRC90 chemical mechanism used for Canadian lower Fraser Valley ozone studies

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