ChemInform Abstract: ENERGY DISPOSAL IN THE PHOTOFRAGMENTATION OF PYRUVIC ACID IN THE GAS PHASE

Abstract. Pyruvic acid, CH3C(O)C(O)OH, is an organic acid of biogenic origin that plays a crucial role in plant metabolism, is present in tropospheric air in both gas-phase and aerosol-phase and is implicated in the formation of secondary organic aerosols (SOA). Up to now, only a few field studies have reported mixing ratios of gas-phase pyruvic acid and its tropospheric sources and sinks are poorly constrained. We present the first gas-phase measurements of pyruvic acid in the boreal forest as part of the IBAIRN (Influence of Biosphere–Atmosphere Interactions on the Reactive Nitrogen budget) field campaign in Hyytiälä, Finland, in September 2016. The mean pyruvic acid mixing ratio during IBAIRN was 96 pptv, with a maximum value of 327 pptv. From our measurements we derived the overall pyruvic acid source strength and quantified the contributions of isoprene oxidation and direct emissions from vegetation in this monoterpene-dominated, forested environment. Further, we discuss the relevance of gas-phase pyruvic acid for atmospheric chemistry by investigating the impact of its photolysis on acetaldehyde and peroxy radical production rates. Our results show that, based on our present understanding of its photo-chemistry, pyruvic acid is an important source of acetaldehyde in the boreal environment, exceeding ethane/propane oxidation by factors of ~ 10 and ~ 20.

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Dynamics of Vibrational Overtone Excited Pyruvic Acid in the Gas Phase: Line Broadening through Hydrogen-Atom Chattering

The Journal of Physical Chemistry A ◽

10.1021/jp803225c ◽

2008 ◽

Vol 112 (32) ◽

pp. 7321-7331 ◽

Cited By ~ 56

Author(s):

Kaito Takahashi ◽

Kathryn L. Plath ◽

Rex T. Skodje ◽

Veronica Vaida

Keyword(s):

Hydrogen Atom ◽

Gas Phase ◽

Pyruvic Acid ◽

Line Broadening ◽

Phase Line ◽

Vibrational Overtone

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Energy disposal in the photofragmentation of pyruvic acid in the gas phase

Journal of the American Chemical Society ◽

10.1021/ja00349a019 ◽

1983 ◽

Vol 105 (11) ◽

pp. 3485-3488 ◽

Cited By ~ 46

Author(s):

Robert N. Rosenfeld ◽

Brad Weiner

Keyword(s):

Gas Phase ◽

Pyruvic Acid

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Atmospheric Simulation Chamber Studies of the Gas-Phase Photolysis of Pyruvic Acid

The Journal of Physical Chemistry A ◽

10.1021/acs.jpca.7b05139 ◽

2017 ◽

Vol 121 (44) ◽

pp. 8348-8358 ◽

Cited By ~ 13

Author(s):

Allison E. Reed Harris ◽

Mathieu Cazaunau ◽

Aline Gratien ◽

Edouard Pangui ◽

Jean-François Doussin ◽

...

Keyword(s):

Gas Phase ◽

Pyruvic Acid ◽

Chamber Studies ◽

Simulation Chamber

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Tropospheric sources and sinks of gas-phase acids in the Colorado Front Range

Atmospheric Chemistry and Physics ◽

10.5194/acp-18-12315-2018 ◽

2018 ◽

Vol 18 (16) ◽

pp. 12315-12327 ◽

Cited By ~ 11

Author(s):

James M. Mattila ◽

Patrick Brophy ◽

Jeffrey Kirkland ◽

Samuel Hall ◽

Kirk Ullmann ◽

...

Keyword(s):

Gas Phase ◽

Pyruvic Acid ◽

Photochemical Reactions ◽

Ionization Mass ◽

Vertical Profiles ◽

Front Range ◽

Alkanoic Acid ◽

Surface Level ◽

Sources And Sinks ◽

Alkanoic Acids

Abstract. We measured organic and inorganic gas-phase acids in the Front Range of Colorado to better understand their tropospheric sources and sinks using a high-resolution time-of-flight chemical ionization mass spectrometer. Measurements were conducted from 4 to 13 August 2014 at the Boulder Atmospheric Observatory during the Front Range Air Pollution and Photochemistry Éxperiment. Diurnal increases in mixing ratios are consistent with photochemical sources of HNO3, HNCO, formic, propionic, butyric, valeric, and pyruvic acid. Vertical profiles taken on the 300 m tower demonstrate net surface-level emissions of alkanoic acids, but net surface deposition of HNO3 and pyruvic acid. The surface-level alkanoic acid source persists through both day and night, and is thus not solely photochemical. Reactions between O3 and organic surfaces may contribute to the surface-level alkanoic acid source. Nearby traffic emissions and agricultural activity are a primary source of propionic, butyric, and valeric acids, and likely contribute photochemical precursors to HNO3 and HNCO. The combined diel and vertical profiles of the alkanoic acids and HNCO are inconsistent with dry deposition and photochemical losses being the only sinks, suggesting additional loss mechanisms.

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Pyruvic acid in the boreal forest: gas-phase mixing ratios and impact on radical chemistry

Atmospheric Chemistry and Physics ◽

10.5194/acp-20-3697-2020 ◽

2020 ◽

Vol 20 (6) ◽

pp. 3697-3711 ◽

Cited By ~ 1

Author(s):

Philipp G. Eger ◽

Jan Schuladen ◽

Nicolas Sobanski ◽

Horst Fischer ◽

Einar Karu ◽

...

Keyword(s):

Boreal Forest ◽

Gas Phase ◽

Atmospheric Chemistry ◽

Pyruvic Acid ◽

Peroxy Radical ◽

Field Studies ◽

Sources And Sinks ◽

Mixing Ratios ◽

Boreal Environment ◽

The Impact

Abstract. Pyruvic acid (CH3C(O)C(O)OH, 2-oxopropanoic acid) is an organic acid of biogenic origin that plays a crucial role in plant metabolism, is present in tropospheric air in both gas-phase and aerosol-phase, and is implicated in the formation of secondary organic aerosols (SOAs). Up to now, only a few field studies have reported mixing ratios of gas-phase pyruvic acid, and its tropospheric sources and sinks are poorly constrained. We present the first measurements of gas-phase pyruvic acid in the boreal forest as part of the IBAIRN (Influence of Biosphere–Atmosphere Interactions on the Reactive Nitrogen budget) field campaign in Hyytiälä, Finland, in September 2016. The mean pyruvic acid mixing ratio during IBAIRN was 96 pptv, with a maximum value of 327 pptv. From our measurements we estimated the overall pyruvic acid source strength and quantified the contributions of isoprene oxidation and direct emissions from vegetation in this monoterpene-dominated forested environment. Further, we discuss the relevance of gas-phase pyruvic acid for atmospheric chemistry by investigating the impact of its photolysis on acetaldehyde and peroxy radical production rates. Our results show that, based on our present understanding of its photochemistry, pyruvic acid is an important source of acetaldehyde in the boreal environment, exceeding ethane and propane oxidation by factors of ∼10 and ∼20.

Download Full-text

Tropospheric sources and sinks of gas-phase acids in the Colorado Front Range

10.5194/acp-2018-326 ◽

2018 ◽

Author(s):

James M. Mattila ◽

Patrick Brophy ◽

Jeffrey Kirkland ◽

Samuel Hall ◽

Kirk Ullmann ◽

...

Keyword(s):

Gas Phase ◽

Pyruvic Acid ◽

Photochemical Reactions ◽

Ionization Mass ◽

Vertical Profiles ◽

Front Range ◽

Alkanoic Acid ◽

Surface Level ◽

Sources And Sinks ◽

Alkanoic Acids

Abstract. We measured organic and inorganic gas-phase acids in the Front Range of Colorado to better understand their tropospheric sources and sinks using a high-resolution time-of-flight chemical ionization mass spectrometer. Measurements were conducted from 4 to 13 August 2014 at the Boulder Atmospheric Observatory during the Front Range Air Pollution and Photochemistry Éxperiment. Diurnal increases in mixing ratios are consistent with photochemical sources of HNO3, HNCO, formic, propionic, butyric, valeric, and pyruvic acid. Vertical profiles taken on the 300 m tower demonstrate net surface-level emissions of alkanoic acids, but net surface deposition of HNO3 and pyruvic acid. The surface-level alkanoic acid source persists through both day and night, and is thus not solely photochemical. Reactions between O3 and organic surfaces may contribute to the surface-level alkanoic acid source. Nearby traffic emissions and agricultural activity are a primary source of propionic, butyric, and valeric acid, and likely contribute photochemical precursors to HNO3 and HNCO. The combined diel and vertical profiles of the alkanoic acids and HNCO are inconsistent with dry deposition and photochemical losses being the only sinks, suggesting additional loss mechanisms.

Download Full-text