Production of methyl vinyl ketone and methacrolein via the hydroperoxyl pathway of isoprene oxidation

Liu, Yingjun; Herdlinger-Blatt, I. S.; McKinney, K. A.; Martin, Scot T.

doi:10.5194/acp-13-5715-2013

Cited by 151 publications

(221 citation statements)

References 59 publications

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“…Liu et al (2013) implemented this technique successfully in their laboratory study using SRI-ToFMS, resulting in a lower yield than previously reported for MAC and MVK in the low-NO oxidation of isoprene. Field application may prove more challenging, however, as the trapping is labor intensive and requires careful humidity control to avoid ice buildup and blockage.…”

Section: Analytical Challengesmentioning

confidence: 99%

“…These uncertainties stem from, for example, the large range in reported yields for isoprene nitrates (4-15 %) (Paulot et al, 2009a), disagreements up to 90 % in reported MAC and MVK yields from the low-NO pathway (Liu et al, 2013, and references therein), various proposed sources of SOA from the high-NO pathway Kjaergaard et al, 2012;Lin et al, 2013), missing contributions to SOA mass from the low-NO pathway , uncharacterized fates of oxidized species like HPALDs (which may have isomer dependence), incomplete understanding of oxygen incorporation (Peeters et al, 2009;Crounse et al, 2013), and under-characterized impact of RO 2 lifetimes on chamber results . The OH oxidation of α-pinene (Eddingsaas et al, 2012) and other monoterpenes is less well characterized than that of isoprene, but, in general, proceeds through analogous steps.…”

Section: Oh Oxidationmentioning

confidence: 99%

“…In general, the decomposition was exacerbated by instruments with harsher sampling conditions, i.e., high ionization energy (e.g., the standard H 3 O + mode of SRI-ToFMS), high temperatures, and/or materials incompatible with organics (e.g., the hot stainless steel sample loop and inlet of GCFID). OVOCs from the low-NO isoprene photooxidation have been shown to decompose to MAC and MVK in commercial PTRMS instruments (Liu et al, 2013), but the exact identities of the compounds were unclear. During FIXCIT, it was observed that ISOPOOH, IEPOX, and pinonaldehyde were detected at m/z 71.050 in the SRI-ToFMS in PTR mode (the sum of MAC + MVK).…”

Section: Analytical Challengesmentioning

confidence: 99%

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Overview of the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT): mechanistic chamber studies on the oxidation of biogenic compounds

et al. 2014

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Abstract. The Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT) was a collaborative atmospheric chamber campaign that occurred during January 2014. FIXCIT is the laboratory component of a synergistic field and laboratory effort aimed toward (1) better understanding the chemical details behind ambient observations relevant to the southeastern United States, (2) advancing the knowledge of atmospheric oxidation mechanisms of important biogenic hydrocarbons, and (3) characterizing the behavior of field instrumentation using authentic standards. Approximately 20 principal scientists from 14 academic and government institutions performed parallel measurements at a forested site in Alabama and at the atmospheric chambers at Caltech. During the 4 week campaign period, a series of chamber experiments was conducted to investigate the dark-and photo-induced oxidation of isoprene, α-pinene, methacrolein, pinonaldehyde, acylperoxy nitrates, isoprene hydroxy nitrates (ISOPN), isoprene hydroxy hydroperoxides (ISOPOOH), and isoprene epoxydiols (IEPOX) in a highly controlled and atmospherically relevant manner. Pinonaldehyde and isomer-specific standards of ISOPN, ISOPOOH, and IEPOX were synthesized and contributed by campaign participants, which enabled explicit exploration into the oxidation mechanisms and instrument responses for these important atmospheric compounds. The present overview describes the goals, experimental design, instrumental techniques, and preliminary observations from the campaign. This work provides context for forthcoming publications affiliated with the FIXCIT campaign. Insights from FIXCIT are anticipated to aid significantly in interpretation of field data and the revision of mechanisms currently implemented in regional and global atmospheric models.

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Section: Analytical Challengesmentioning

confidence: 99%

Section: Oh Oxidationmentioning

confidence: 99%

Section: Analytical Challengesmentioning

confidence: 99%

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Overview of the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT): mechanistic chamber studies on the oxidation of biogenic compounds

et al. 2014

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“…During the dry season the ratio of methyl vinyl ketone + methacrolein + hydroperoxides (MVK + MAC + ISOPOOH) (Liu et al, 2013) to isoprene was higher compared to the dry-to-wet transition and the wet season (data not shown). This higher ratio may indicate an increased oxidative capacity of the atmosphere during the dry season.…”

Section: Seasonal Variation On Isoprenoid Mixing Ratios and Emissionsmentioning

confidence: 99%

Seasonality of isoprenoid emissions from a primary rainforest in central Amazonia

Alves¹,

Jardine²,

Tóta³

et al. 2016

Atmos. Chem. Phys.

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Abstract. Tropical rainforests are an important source of isoprenoid and other volatile organic compound (VOC) emissions to the atmosphere. The seasonal variation of these compounds is however still poorly understood. In this study, vertical profiles of mixing ratios of isoprene, total monoterpenes and total sesquiterpenes, were measured within and above the canopy, in a primary rainforest in central Amazonia, using a proton transfer reaction -mass spectrometer (PTR-MS). Fluxes of these compounds from the canopy into the atmosphere were estimated from PTR-MS measurements by using an inverse Lagrangian transport model. Measurements were carried out continuously from September 2010 to January 2011, encompassing the dry and wet seasons. Mixing ratios were higher during the dry (isoprene -2.68 ± 0.9 ppbv, total monoterpenes -0.67 ± 0.3 ppbv; total sesquiterpenes -0.09 ± 0.07 ppbv) than the wet season (isoprene -1.66 ± 0.9 ppbv, total monoterpenes -0.47 ± 0.2 ppbv; total sesquiterpenes -0.03±0.02 ppbv) for all compounds. Ambient air temperature and photosynthetically active radiation (PAR) behaved similarly. Daytime isoprene and total monoterpene mixing ratios were highest within the canopy, rather than near the ground or above the canopy. By comparison, daytime total sesquiterpene mixing ratios were highest near the ground. Daytime fluxes varied significantly between seasons for all compounds. The maximums for isoprene (2.53 ± 0.5 µmol m −2 h −1 ) and total monoterpenes (1.77 ± 0.05 µmol m −2 h −1 ) were observed in the late dry season, whereas the maximum for total sesquiterpenes Published by Copernicus Publications on behalf of the European Geosciences Union. E. G. Alves et al.: Seasonality of isoprenoid emissions from a primary rainforest, Amazoniawas found during the dry-to-wet transition season (0.77 ± 0.1 µmol m −2 h −1 ). These flux estimates suggest that the canopy is the main source of isoprenoids emitted into the atmosphere for all seasons. However, uncertainties in turbulence parameterization near the ground could affect estimates of fluxes that come from the ground. Leaf phenology seemed to be an important driver of seasonal variation of isoprenoid emissions. Although remote sensing observations of changes in leaf area index were used to estimate leaf phenology, MEGAN 2.1 did not fully capture the behavior of seasonal emissions observed in this study. This could be a result of very local effects on the observed emissions, but also suggest that other parameters need to be better determined in biogenic volatile organic compound (BVOC) models. Our results support established findings that seasonality of isoprenoids are driven by seasonal changes in light, temperature and leaf phenology. However, they suggest that leaf phenology and its role on isoprenoid production and emission from tropical plant species needs to be better understood in order to develop mechanistic explanations for seasonal variation in emissions. This also may reduce the uncertainties of model estimates associated with the responses to en...

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“…The new scheme also includes an update for the aerosol reactive uptake coefficient of NO 3 radicals, in which the value is increased from 10 −4 to 0.1 (Mao et al, 2013b). Beyond Mao et al (2013b), we also change the stoichiometry of the (ISOPO 2 + HO 2 ) reaction to that recommended by the laboratory study of Liu et al (2013), which has smaller uncertainties and leads to relatively smaller yields (by ∼ 50 %) of HO x , methyl vinyl ketone, and methacrolein from this pathway. Our work tests the sensitivity of model results to these updates in the isoprene photo-oxidation mechanism.…”

Section: Isoprene Photo-oxidation Mechanismmentioning

confidence: 99%

Uncertainties in isoprene photochemistry and emissions: implications for the oxidative capacity of past and present atmospheres and for climate forcing agents

et al. 2015

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Abstract. Isoprene and its oxidation products are major players in the oxidative chemistry of the troposphere. Current understanding of the factors controlling biogenic isoprene emissions and of the fate of isoprene oxidation products in the atmosphere has been evolving rapidly. We use a climate-biosphere-chemistry modeling framework to evaluate the sensitivity of estimates of the tropospheric oxidative capacity to uncertainties in isoprene emissions and photochemistry. Our work focuses on two climate transitions: from the Last Glacial Maximum (LGM, 19 000-23 000 years BP) to the preindustrial (1770s) and from the preindustrial to the present day (1990s). We find that different oxidants have different sensitivities to the uncertainties tested in this study. Ozone is relatively insensitive, whereas OH is the most sensitive: changes in the global mean OH levels for the LGM-to-preindustrial transition range between −29 and +7 % and those for the preindustrial-to-present-day transition range between −8 and +17 % across our simulations. We find little variability in the implied relative LGMpreindustrial difference in methane emissions with respect to the uncertainties tested in this study. Conversely, estimates of the preindustrial-to-present-day and LGM-to-preindustrial changes in the global burden of secondary organic aerosol (SOA) are highly sensitive. We show that the linear relationship between tropospheric mean OH and tropospheric mean ozone photolysis rates, water vapor, and total emissions of NO x and reactive carbon -first reported in Murray et al. (2014) -does not hold across all periods with the new isoprene photochemistry mechanism. This study demonstrates how inadequacies in our current understanding of isoprene emissions and photochemistry impede our ability to constrain the oxidative capacities of the present and past atmospheres, its controlling factors, and the radiative forcing of some short-lived species such as SOA over time.

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Production of methyl vinyl ketone and methacrolein via the hydroperoxyl pathway of isoprene oxidation

Cited by 151 publications

References 59 publications

Overview of the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT): mechanistic chamber studies on the oxidation of biogenic compounds

Overview of the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT): mechanistic chamber studies on the oxidation of biogenic compounds

Seasonality of isoprenoid emissions from a primary rainforest in central Amazonia

Uncertainties in isoprene photochemistry and emissions: implications for the oxidative capacity of past and present atmospheres and for climate forcing agents

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