Unique products of the reaction of isoprene with atomic chlorine: Potential markers of chlorine atom chemistry

Nordmeyer, Trent; Wang, Weihong; Ragains, Mark L.; Finlayson-Pitts, Barbara J.; Spicer, C. W.; Plastridge, Robert A.

doi:10.1029/97gl01547

Cited by 44 publications

(66 citation statements)

References 27 publications

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“…S12). The formation of C 5 H 8 O from chlorine-isoprene oxidation has been proposed in the literature (Nordmeyer et al, 1997). Previous studies that observed C 5 H 8 O during OH-initiated oxidation of isoprene identified it as 2-methylbut-3-enal, but its formation mechanism remains unclear (Brégonzio-Rozier et al, 2015;Healy et al, 2008) and is beyond the scope of this work.…”

Section: Soa Yieldmentioning

confidence: 79%

“…Previous studies that observed C 5 H 8 O during OH-initiated oxidation of isoprene identified it as 2-methylbut-3-enal, but its formation mechanism remains unclear (Brégonzio-Rozier et al, 2015;Healy et al, 2008) and is beyond the scope of this work. It should be noted that CMBO has long been identified as a unique gas-phase marker for isoprene-chlorine oxidation (Chang and Allen, 2006;Nordmeyer et al, 1997;Riemer et al, 2008;Tanaka et al, 2003). Degradation of CMBO by OH is implemented in some air quality models, though only with inferred reaction rates ).…”

Section: Soa Yieldmentioning

confidence: 99%

“…Chlorine-initiated oxidation of isoprene could either proceed via the dominant (85 %) chlorine-addition pathway or a minor (15 %) hydrogen-abstraction pathway (Fantechi et al, 1998;Lei and Zhang, 2000;Nordmeyer et al, 1997;Orlando et al, 2003). Major gas-phase products include methyl vinyl ketone (MVK), methacrolein (MACR), chloroacetone, chloroacetaldehyde, hydrochloric acid, and isomers of 1-chloro-3-methyl-3-butene-2-one (CMBO), a unique tracer for atmospheric chlorine chemistry (Nordmeyer et al, 1997;Riemer et al, 2008;Tanaka et al, 2003).…”

Section: S Wang and L Hildebrandt Ruiz: Secondary Organic Aerosomentioning

confidence: 99%

“…Major gas-phase products include methyl vinyl ketone (MVK), methacrolein (MACR), chloroacetone, chloroacetaldehyde, hydrochloric acid, and isomers of 1-chloro-3-methyl-3-butene-2-one (CMBO), a unique tracer for atmospheric chlorine chemistry (Nordmeyer et al, 1997;Riemer et al, 2008;Tanaka et al, 2003). The rate constant of the isoprene-chlorine reaction at 25 • C (2.64-5.50 × 10 −10 molecules −1 cm 3 ; Fantechi et al, 1998;Orlando et al, 2003;Ragains and Finlayson-Pitts, 1997) is much larger than the rate constant of the isoprene-OH reaction (1.00 × 10 −10 molecules −1 cm 3 ; Atkinson and Arey, 2003), suggesting that isoprene-chlorine chemistry could compete with isoprene-OH chemistry under certain conditions.…”

Section: S Wang and L Hildebrandt Ruiz: Secondary Organic Aerosomentioning

confidence: 99%

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Secondary organic aerosol from chlorine-initiated oxidation of isoprene

Wang

Ruiz

2017

Atmos. Chem. Phys.

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Abstract. Recent studies have found concentrations of reactive chlorine species to be higher than expected, suggesting that atmospheric chlorine chemistry is more extensive than previously thought. Chlorine radicals can interact with hydroperoxy (HO x ) radicals and nitrogen oxides (NO x ) to alter the oxidative capacity of the atmosphere. They are known to rapidly oxidize a wide range of volatile organic compounds (VOCs) found in the atmosphere, yet little is known about secondary organic aerosol (SOA) formation from chlorineinitiated photooxidation and its atmospheric implications. Environmental chamber experiments were carried out under low-NO x conditions with isoprene and chlorine as primary VOC and oxidant sources. Upon complete isoprene consumption, observed SOA yields ranged from 7 to 36 %, decreasing with extended photooxidation and SOA aging. Formation of particulate organochloride was observed. A highresolution time-of-flight chemical ionization mass spectrometer was used to determine the molecular composition of gasphase species using iodide-water and hydronium-water cluster ionization. Multi-generational chemistry was observed, including ions consistent with hydroperoxides, chloroalkyl hydroperoxides, isoprene-derived epoxydiol (IEPOX), and hypochlorous acid (HOCl), evident of secondary OH production and resulting chemistry from Cl-initiated reactions. This is the first reported study of SOA formation from chlorineinitiated oxidation of isoprene. Results suggest that tropospheric chlorine chemistry could contribute significantly to organic aerosol loading.

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Section: Soa Yieldmentioning

confidence: 79%

Section: Soa Yieldmentioning

confidence: 99%

Section: S Wang and L Hildebrandt Ruiz: Secondary Organic Aerosomentioning

confidence: 99%

Section: S Wang and L Hildebrandt Ruiz: Secondary Organic Aerosomentioning

confidence: 99%

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Secondary organic aerosol from chlorine-initiated oxidation of isoprene

Wang

Ruiz

2017

Atmos. Chem. Phys.

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“…Isoprene and the monoterpenes are also quite reactive and have atmospheric lifetimes of considerably less than a day. Like most VOC, the daytime oxidation of biogenic VOC is initiated primarily by reaction with OH, however reaction with O 3 , NO 3 , and Cl can also be important under some circumstances for some compounds (Atkinson, 1994(Atkinson, , 1997Atkinson and Arey, 1998;Nordmeyer et al, 1997;Paulson et al, 1992a, b).…”

Section: Speciationmentioning

confidence: 99%

Past and present-day biogenic volatile organic compound emissions in East Asia

Steiner

Luo

Huang

2002

Atmospheric Environment

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Biogenic volatile organic carbon (VOC) emissions from vegetation in East Asia are estimated for two contrasting land-cover scenarios: near present-day conditions derived from satellite data and pre-disturbed land-cover based on climatological parameters and plant functional type. Hourly fluxes of isoprene and monoterpenes are calculated on a grid of 60 km Â 60 km cells covering much of East Asia using meteorological conditions derived from a 12-month simulation of the region using regional climate model, monthly leaf area indexes, and the Guenther et al. (J. Geophys. Res. 101 (1995) 1345) ecosystem-dependent emission factors. Total present-day isoprene emissions are estimated at approximately 12 Tg C yr À1 and monoterpene emissions at 6 Tg C yr À1 . These emissions are approximately 5.4 and 4 Tg C yr À1 lower than the estimated pre-disturbed emissions of isoprene and monoterpenes, respectively, largely due to the conversion of forested land to cropland. ORVOC emission estimates for the present-day scenario, obtained by assuming a constant ORVOC emission factor for all ecosystems, are slightly higher in magnitude than isoprene emissions. Present-day totals of combined biogenic and anthropogenic VOC emissions are generally larger than biogenic VOC emissions in the pre-disturbed scenario, indicating that human activities have led to a net increase in the atmospheric source of VOC in East Asia. r

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Rate coefficients and mechanisms of the reaction of cl‐atoms with a series of unsaturated hydrocarbons under atmospheric conditions

Orlando

Tyndall

Apel

et al. 2003

Int J of Chemical Kinetics

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Rate coefficients and/or mechanistic information are provided for the reaction of Clatoms with a number of unsaturated species, including isoprene, methacrolein (MACR), methyl vinyl ketone (MVK), 1,3-butadiene, trans-2-butene, and 1-butene. The following Cl-atom rate coefficients were obtained at 298 K near 1 atm total pressure: k(isoprene) = (4.3 ± 0.6) × 10 −10 cm 3 molecule −1 s −1 (independent of pressure from 6.2 to 760 Torr); k(MVK) = (2.2 ± 0.3) × 10 −10 cm 3 molecule −1 s −1 ; k(MACR) = (2.4 ± 0.3) × 10 −10 cm 3 molecule −1 s −1 ; k(trans-2-butene) = (4.0 ± 0.5) × 10 −10 cm 3 molecule −1 s −1 ; k(1-butene) = (3.0 ± 0.4) × 10 −10 cm 3 molecule −1 s −1 . Products observed in the Cl-atom-initiated oxidation of the unsaturated species at 298 K in 1 atm air are as follows (with % molar yields in parentheses): CH 2 O (9.5 ± 1.0%), HCOCl (5.1 ± 0.7%), and 1-chloro-3-methyl-3-buten-2-one (CMBO, not quantified) from isoprene; chloroacetaldehyde (75 ± 8%), CO 2 (58 ± 5%), CH 2 O (47 ± 7%), CH 3 OH (8%), HCOCl (7 ± 1%), and peracetic acid (6%) from MVK; CO (52 ± 4%), chloroacetone (42 ± 5%), CO 2 (23 ± 2%), CH 2 O (18 ± 2%), and HCOCl (5%) from MACR; CH 2 O (7 ± 1%), HCOCl (3%), acrolein (≈3%), and 4-chlorocrotonaldehyde (CCA, not quantified) from 1,3-butadiene; CH 3 CHO (22 ± 3%), CO 2 (13 ± 2%), 3-chloro-2-butanone (13 ± 4%), CH 2 O (7.6 ± 1.1%), and CH 3 OH (1.8 ± 0.6%) from trans-2-butene; and chloroacetaldehyde (20 ± 3%), CH 2 O (7 ± 1%), CO 2 (4 ± 1%), RATE COEFFICIENTS AND MECHANISMS OF THE REACTION OF Cl-ATOMS 335and HCOCl (4 ± 1%) from 1-butene. Product yields from both trans-2-butene and 1-butene were found to be O 2 -dependent. In the case of trans-2-butene, the observed O 2 -dependence is the result of a competition between unimolecular decomposition of the CH 3 CH(Cl) CH(O • ) CH 3 radical and its reaction with O 2 , with k decomp /k O2 = (1.6 ± 0.4) × 10 19 molecule cm −3 . The activation energy for decomposition is estimated at 11.5 ± 1.5 kcal mol −1 . The variation of the product yields with O 2 in the case of 1-butene results from similar competitive reaction pathways for the two β-chlorobutoxy radicals involved in the oxidation, ClCH 2 CH(O • )CH

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Unique products of the reaction of isoprene with atomic chlorine: Potential markers of chlorine atom chemistry

Cited by 44 publications

References 27 publications

Secondary organic aerosol from chlorine-initiated oxidation of isoprene

Secondary organic aerosol from chlorine-initiated oxidation of isoprene

Past and present-day biogenic volatile organic compound emissions in East Asia

Rate coefficients and mechanisms of the reaction of cl‐atoms with a series of unsaturated hydrocarbons under atmospheric conditions

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