Product Quantum Yields for the 350 nm Photodecomposition of Pyruvic Acid in Air

Berges, Markus; Warneck, Peter

doi:10.1002/bbpc.19920960334

Cited by 35 publications

(73 citation statements)

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“…The boreal forest is one of the largest terrestrial biomes on Earth, covering about 10 % of its land surface and emitting large amounts of biogenic volatile organic compounds (VOCs) into the atmosphere (Kesselmeier and Staudt, 1999;Rinne et al, 2005;Hakola et al, 2012). It serves as an important global carbon reservoir (Bradshaw and Warkentin, 2015) and impacts the Earth's climate not only through forestatmosphere carbon exchange but also via surface albedo, evapotranspiration, and formation of cloud condensation nuclei and SOA from gaseous biogenic precursors (Kulmala et al, 2004;Bonan, 2008;Sihto et al, 2011). Our work focuses on the first measurement and chemical impact of gas-phase pyruvic acid in a boreal forest environment.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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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.

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Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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“…So far, to calculate the photo-dissociation rate constant for pyruvic acid (Jpyr) we have used the IUPAC recommendation of an overall quantum yield of 0.2 at atmospheric pressure. There are however several inconsistencies in the experimental data sets on pyruvic acid photolysis, with two groups reporting quantum yields that are a factor of ~ 4 larger at this pressure (Berges and Warneck, 1992;Reed Harris et al, 2017). If these large quantum yields were to be correct, the calculated 20 production rates of CH3CHO and CH3C(O)O2 would increase by a factor of 4 (see Table 2) so that PCH3CHO = 28 pptv h -1 (Table 2).…”

Section: Role Of Pyruvic Acid In the Tropospherementioning

confidence: 99%

Pyruvic acid in the boreal forest: first measurements and impact on radical chemistry

Eger¹,

Schuladen²,

Sobanski³

et al. 2019

Preprint

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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 15 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 20 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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“…Quantum effi ciencies have also been determined for pyruvic acid [67], several chlorobenzenes [68] and organic nitrates [69,70]. The few data available are compiled in Chapter 3.…”

Section: Winter (January)mentioning

confidence: 99%

Abiotic Degradation in the Atmosphere

Klöpffer¹,

Wagner²

2007

Atmospheric Degradation of Organic Substances

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1)A sink is defi ned here as an irreversible chemical, photochemical or biochemical reaction which removes a molecule from the environment; a perfect sink leads to mineralization. Within this defi nition, the transfer to and the temporary fi xation in another compartment (e.g., soil, vegetation or water) without chemical modifi cation is not considered to be a sink [1].2 Photo-degradation in the Homogenous Gas Phase of the Troposphere Chapter 2: Abiotic Degradation in the Atmosphere 28 k OH (T) = (2.25 + 0.46 -0.39) × 10 -18 T 2 exp{(-910 ± 56)/T} cm 3 molecule -1 s -1 k OH (298 K) = 9.43 × 10 -15 cm 3 molecule -1 s -1More interesting for the average OH lifetime is k OH at the (weighted or effective) average temperature of the troposphere. This temperature has been estimated by Warneck [15] in an analysis of the tropospheric CH 4 + OH reaction as eff = 280 K. According to an earlier estimate, based on the lifetime of chlorinated hydrocarbons [34], this temperature may be as low as 260 K. Using the more recent estimate by Warneck, we obtain k OH (280 K) = 6.84 × 10 -15 cm 3 molecule -1 s -1The average tropospheric OH lifetimes of MCF is calculated to be τ OH = 9.3 a This value is higher than the average residence times calculated for MCF, which are based on long-term measurements of MCF concentrations and estimates of the amounts emitted yearly (see Section 5).MCF is photolysed at wavelengths around 200 nm [28] and can therefore act as a source of chlorine atoms in the stratosphere and contribute to ozone destruction. It has been phased out as a result of the Protocol of Montreal and its follow-up agreements.An up-to-date data collection of OH-reaction rate constants can be found in Chapter 3. Earlier critical data collections are mostly attributable to Roger Atkinson, whose group also measured many substances for the fi rst time

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Product Quantum Yields for the 350 nm Photodecomposition of Pyruvic Acid in Air

Cited by 35 publications

References 10 publications

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

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

Pyruvic acid in the boreal forest: first measurements and impact on radical chemistry

Abiotic Degradation in the Atmosphere

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