HCO Quantum Yields in the Photolysis of HC(O)C(O)H (Glyoxal) between 290 and 420 nm

Feierabend, Karl J.; Flad, Jonathan E.; Brown, Steven S.; Burkholder, James B.

doi:10.1021/jp9033003

Cited by 27 publications

(41 citation statements)

References 36 publications

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“…Although actinic flux spectra were recorded to calculate photolysis loss rate coefficients ( j ) for species such as NO 2 and O 3 , j CHOCHO has not been reported to date for the Pasadena ground site. Using actinic flux spectra acquired onboard the NOAA WP‐3D aircraft, we calculated j CHOCHO [ Feierabend et al , 2009], and parameterized its empirical relationship to j NO2 and j O3 to be j CHOCHO = j NO2 × (0.010910 ± 3 × 10 −6 ) + j O3 × (0.6039 ± 0.0006). This particular parameterization was chosen because the action spectrum (product of absorption and quantum yield) for glyoxal lies spectrally between the action spectra of O 3 and NO 2 .…”

Section: Resultsmentioning

confidence: 99%

The glyoxal budget and its contribution to organic aerosol for Los Angeles, California, during CalNex 2010

et al. 2011

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[1] Recent laboratory and field studies have indicated that glyoxal is a potentially large contributor to secondary organic aerosol mass. We present in situ glyoxal measurements acquired with a recently developed, high sensitivity spectroscopic instrument during the CalNex 2010 field campaign in Pasadena, California. We use three methods to quantify the production and loss of glyoxal in Los Angeles and its contribution to organic aerosol. First, we calculate the difference between steady state sources and sinks of glyoxal at the Pasadena site, assuming that the remainder is available for aerosol uptake. Second, we use the Master Chemical Mechanism to construct a two-dimensional model for gas-phase glyoxal chemistry in Los Angeles, assuming that the difference between the modeled and measured glyoxal concentration is available for aerosol uptake. Third, we examine the nighttime loss of glyoxal in the absence of its photochemical sources and sinks. Using these methods we constrain the glyoxal loss to aerosol to be 0-5 × 10 −5 s −1 during clear days and (1 ± 0.3) × 10 −5 s −1 at night. Between 07:00-15:00 local time, the diurnally averaged secondary organic aerosol mass increases from 3.2 mg m −3 to a maximum of 8.8 mg m −3 . The constraints on the glyoxal budget from this analysis indicate that it contributes 0-0.2 mg m −3 or 0-4% of the secondary organic aerosol mass.

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Section: Resultsmentioning

confidence: 99%

The glyoxal budget and its contribution to organic aerosol for Los Angeles, California, during CalNex 2010

et al. 2011

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“…Its sources include direct emissions from biofuel use and biomass burning and secondary production from oxidation of various volatile organic compounds (VOCs) [ Fu et al ., ; Hays et al ., ; Myriokefalitakis et al ., ]. Glyoxal has a lifetime of about 1–3 h against photolysis and oxidation by OH at midday [ Feierabend et al ., ; Volkamer et al ., ; Washenfelder et al ., ]. It is highly water soluble, with a Henry's law constant of 3.0–4.2 × 10 5 M atm −1 at 298 K [ Sander , ].…”

Section: Introductionmentioning

confidence: 99%

Observational constraints on glyoxal production from isoprene oxidation and its contribution to organic aerosol over the Southeast United States

Mao

Min

et al. 2016

JGR Atmospheres

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We use a 0‐D photochemical box model and a 3‐D global chemistry‐climate model, combined with observations from the NOAA Southeast Nexus (SENEX) aircraft campaign, to understand the sources and sinks of glyoxal over the Southeast United States. Box model simulations suggest a large difference in glyoxal production among three isoprene oxidation mechanisms (AM3ST, AM3B, and Master Chemical Mechanism (MCM) v3.3.1). These mechanisms are then implemented into a 3‐D global chemistry‐climate model. Comparison with field observations shows that the average vertical profile of glyoxal is best reproduced by AM3ST with an effective reactive uptake coefficient γglyx of 2 × 10−3 and AM3B without heterogeneous loss of glyoxal. The two mechanisms lead to 0–0.8 µg m−3 secondary organic aerosol (SOA) from glyoxal in the boundary layer of the Southeast U.S. in summer. We consider this to be the lower limit for the contribution of glyoxal to SOA, as other sources of glyoxal other than isoprene are not included in our model. In addition, we find that AM3B shows better agreement on both formaldehyde and the correlation between glyoxal and formaldehyde (RGF = [GLYX]/[HCHO]), resulting from the suppression of δ‐isoprene peroxy radicals. We also find that MCM v3.3.1 may underestimate glyoxal production from isoprene oxidation, in part due to an underestimated yield from the reaction of isoprene epoxydiol (IEPOX) peroxy radicals with HO2. Our work highlights that the gas‐phase production of glyoxal represents a large uncertainty in quantifying its contribution to SOA.

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“…11,12 In addition, (HCO) 2 photochemistry is a recognised source of HOx (OH and HO 2 ) radicals in the troposphere. [13][14][15] (HCO) 2 is removed from the troposphere within a few hours, during daylight its atmospheric lifetime is largely determined by the rates of photolysis and reaction with OH: 13, [16][17][18] (HCO) 2 + hv  2HCO or HCHO + CO (R1) (HCO) 2 + OH  HC(O)CO + H 2 O (R2)…”

Section: Introductionmentioning

confidence: 99%

Mechanism of the Reaction of OH with Alkynes in the Presence of Oxygen

et al. 2013

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The kinetics of the OH + glyoxal, (HCO) 2 , reaction have been studied in N 2 and N 2 /O 2 bath gas from 5 80 Torr total pressure and 212 295 K, by monitoring the OH decay via laser induced fluorescence (LIF) in excess (HCO) 2 . The following rate coefficients, k OH + (HCO)2 = (9.7 ± 1.2), (12.2 ± 1.6) and (15.4 ± 2.0) × 10 -12 cm 3 molecule -1 s -1 (where errors represent a combination of statistical error errors) were measured in nitrogen at temperatures of 295, 250 and 212 K, respectively. Rate coefficient measurements were observed to be independent of total pressure, but decreased following addition of O 2 to the reaction cell, consistent with direct OH recycling.OH yields, OH , for this reaction were quantified experimentally for the first time as a function of total pressure, temperature and O 2 concentration. The experimental results have been parameterised using a chemical scheme where a fraction of the HC(O)CO population promptly dissociates to HCO + CO, the remaining HC(O)CO either dissociates thermally or reacts with O 2 to give CO 2 , CO and regenerate OH. A maximum OH of (0.38 ± 0.02) was observed at 212 K, independent of total pressure, suggesting that ~60 % of the HC(O)CO population promptly dissociates upon formation. Qualitatively similar behaviour is observed at 250 K, with a maximum OH of (0.31 ± 0.03); at 295 K the maximum OH decreased further to (0.29 ± 0.03). F OH OH = 0.19 is calculated for 295 K and 1 atm of air. It is shown that the proposed mechanism is consistent with previous chamber studies. Whilst the fits are robust, experimental evidence suggests that the system is influenced by chemical activation and cannot be fully described by thermal rate coefficients. The atmospheric implications of the measurements are briefly discussed.

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HCO Quantum Yields in the Photolysis of HC(O)C(O)H (Glyoxal) between 290 and 420 nm

Cited by 27 publications

References 36 publications

The glyoxal budget and its contribution to organic aerosol for Los Angeles, California, during CalNex 2010

The glyoxal budget and its contribution to organic aerosol for Los Angeles, California, during CalNex 2010

Observational constraints on glyoxal production from isoprene oxidation and its contribution to organic aerosol over the Southeast United States

Mechanism of the Reaction of OH with Alkynes in the Presence of Oxygen

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