Photo-tautomerization of acetaldehyde as a photochemical source of formic acid in the troposphere

Shaw, Miranda F.; Sztáray, Bálint; Whalley, Lisa K.; Heard, Dwayne E.; Millet, Dylan B.; Jordan, Meredith J. T.; Osborn, David L.; Kable, Scott H.

doi:10.1038/s41467-018-04824-2

Cited by 47 publications

(83 citation statements)

References 58 publications

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“…• Figure S2 • Figure S3 1-50% (Larsen et al, 2001;Lee, Goldstein, Kroll, et al, 2006), depending on the species; average yields of 16% (OH) and 8% (ozonolysis) have been assumed in recent large-scale modeling studies (Millet et al, 2015;Paulot et al, 2011). Additional known secondary HCOOH sources include OH-driven oxidation of terminal alkynes (Hatakeyama et al, 1986) and photo-tautomerization of acetaldehyde followed by oxidation of the resulting enol (Millet et al, 2015;Peeters et al, 2015;Shaw et al, 2018).…”

Section: Supporting Informationmentioning

confidence: 99%

Oxidation of Volatile Organic Compounds as the Major Source of Formic Acid in a Mixed Forest Canopy

Alwe

Millet

Chen

et al. 2019

Geophysical Research Letters

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Formic acid (HCOOH) is among the most abundant carboxylic acids in the atmosphere, but its budget is poorly understood. We present eddy flux, vertical gradient, and soil chamber measurements from a mixed forest and apply the data to better constrain HCOOH source/sink pathways. While the cumulative above‐canopy flux was downward, HCOOH exchange was bidirectional, with extended periods of net upward and downward flux. Net above‐canopy fluxes were mostly upward during warmer/drier periods. The implied gross canopy HCOOH source corresponds to 3% and 38% of observed isoprene and monoterpene carbon emissions and is 15× underestimated in a state‐of‐science atmospheric model (GEOS‐Chem). Gradient and soil chamber measurements identify the canopy layer as the controlling source of HCOOH or its precursors to the forest environment; below‐canopy sources were minor. A correlation analysis using an ensemble of marker volatile organic compounds suggests that secondary formation, not direct emission, is the major source driving ambient HCOOH.

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Section: Supporting Informationmentioning

confidence: 99%

Oxidation of Volatile Organic Compounds as the Major Source of Formic Acid in a Mixed Forest Canopy

Alwe

Millet

Chen

et al. 2019

Geophysical Research Letters

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“…Vinyl alcohol (VA), originally proposed as possible source of formic acid by Archibald et al (2007), received full attention when acetaldehyde phototautomerization to VA was shown in the laboratory to be efficient (Andrews et al, 2012) and represent a sizable source of formic acid of the order of 3 TgC/yr (Cady-Perreira et al, 2014;Millet et al, 2015). However, a recent, more detailed experimental evaluation of the phototautomerization yield led to a downward revision of the global source to about 0.8 TgC/yr (Shaw et al, 2018), in good agreement with our model calculations (Table 5). This source could be even lower if VA tautomerizes back to acetaldehyde (da , but acid-catalyzed VA tautomerization was shown to be negligible, and aerosol-mediated tautomerization remains speculative (Peeters et al, 2015).…”

Section: Global Budget Of Formic and Acetic Acidmentioning

confidence: 99%

Chemistry and deposition in the Model of Atmospheric composition at Global and Regional scales using Inversion Techniques for Trace gas Emissions (MAGRITTEv1.0). Part A. Chemical mechanism

Müller¹,

Stavrakou²,

Peeters³

2018

Preprint

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Abstract. A new chemical mechanism for the oxidation of biogenic volatile organic compounds (BVOCs) is presented and implemented in the Model of Atmospheric composition at Global and Regional scales using Inversion Techniques for Trace gas Emissions (MAGRITTE v1.0). With a total of 99 organic species and over 240 gas-phase reactions, 67 photodissociations and 7 heterogeneous reactions, the mechanism treats the chemical degradation of isoprene – its main focus – as well as acetaldehyde, acetone, methylbutenol and the family of monoterpenes. Regarding isoprene, the mechanism incorporates a state-of-the-art representation of its oxidation scheme accounting for all major advances put forward in recent theoretical and laboratory studies. The model and its chemical mechanism are evaluated against the suite of chemical measurements from the SEAC4RS (Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys) airborne campaign, demonstrating a good overall agreement for major isoprene oxidation products, although the aerosol hydrolysis of tertiary and non-tertiary nitrates remain poorly constrained. The comparisons for methylnitrate indicate a very low nitrate yield (

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“…Biomass burning, i.e., combustion of any nonfossilized vegetation, leads to an estimated 60-400 Tg yr −1 of emitted VOCs, though with high uncertainty regarding potential unidentified and/or unmeasured pyrogenic compounds (Giglio et al, 2013;Akagi et al, 2011;Wiedinmyer et al, 2011;Andreae and Merlet, 2001). Ocean-atmosphere VOC fluxes have been investigated with a range of aircraft-and ship-based observations, remote sensing, and modeling approaches for species including isoprene and monoterpenes, other light hydrocarbons, halogenated species, and oxygenated VOCs such as methanol, acetone, formaldehyde, acetaldehyde, glyoxal, and carboxylic acids Kim et al, 2017;Mungall et al, 2017;Coburn et al, 2014;Yang et al, 2013Yang et al, , 2014aBeale et al, 2011Beale et al, , 2013Fischer et al, 2012;Luo and Yu, 2010;Millet et al, , 2010Shaw et al, 2010;Read et al, 2008;Palmer and Shaw, 2005;Williams et al, 2004;Singh et al, 2003;Broadgate et al, 1997;Zhou and Mopper, 1997;Kanakidou et al, 1988). However, the quantitative role of the ocean as a net global VOC source or sink remains uncertain Read et al, 2012).…”

Section: Introductionmentioning

confidence: 99%

“…Through their influence on the hydroxyl radical (OH), VOCs alter the lifetime of long-lived greenhouse gases ( Cubasch et al, 2013 ), while their oxidation products such as ozone (O 3 ) and secondary organic aerosol (SOA) degrade human and ecosystem health ( EPA, 2018 ) and alter Earth’s radiative balance ( Myhre et al, 2013 ). There are large uncertainties associated with the emissions ( Karl et al, 2018 ; Hatch et al, 2017 ; Guenther et al, 2012 ), chemical processing ( Caravan et al, 2018 ; Shaw et al, 2018 ; J. F. Müller et al, 2016 ), and sinks of atmospheric VOCs ( Iavorivska et al, 2017 ; Nguyen et al, 2015 ; Wolfe et al, 2015 ; Karl et al, 2010 ). An ensemble of recent airborne campaigns over North America together afford the most expansive picture yet of the atmospheric VOC distribution over this region.…”

Section: Introductionmentioning

confidence: 99%

On the sources and sinks of atmospheric VOCs: an integrated analysis of recent aircraft campaigns over North America

et al. 2019

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Abstract. We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to (i) characterize the VOC budget and (ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70 % and 95 % of annually emitted VOC carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2× larger source of nonmethane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half of the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC abundance (R2=0.36) and reactivity (R2=0.54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (∼ 60 %), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL : FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene + oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation.

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Photo-tautomerization of acetaldehyde as a photochemical source of formic acid in the troposphere

Cited by 47 publications

References 58 publications

Oxidation of Volatile Organic Compounds as the Major Source of Formic Acid in a Mixed Forest Canopy

Oxidation of Volatile Organic Compounds as the Major Source of Formic Acid in a Mixed Forest Canopy

Chemistry and deposition in the Model of Atmospheric composition at Global and Regional scales using Inversion Techniques for Trace gas Emissions (MAGRITTEv1.0). Part A. Chemical mechanism

On the sources and sinks of atmospheric VOCs: an integrated analysis of recent aircraft campaigns over North America

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