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

2018 ◽  
Vol 18 (16) ◽  
pp. 12315-12327 ◽  
Author(s):  
James M. Mattila ◽  
Patrick Brophy ◽  
Jeffrey Kirkland ◽  
Samuel Hall ◽  
Kirk Ullmann ◽  
...  

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.

2018 ◽  
Author(s):  
James M. Mattila ◽  
Patrick Brophy ◽  
Jeffrey Kirkland ◽  
Samuel Hall ◽  
Kirk Ullmann ◽  
...  

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.


Author(s):  
Natalie G.K. Wong ◽  
Chris Rhodes ◽  
Caroline E.H. Dessent

The application of electrospray ionization mass spectrometry (ESI-MS) as a direct method for detecting reactive intermediates is a technique of developing importance in the routine monitoring of solution-phase reaction pathways. Here, we utilize a novel on-line photolysis ESI-MS approach to detect the photoproducts of riboflavin in aqueous solution under mildly alkaline conditions. Riboflavin is a constituent of many food products, so its breakdown processes are of wide interest. Our on-line photolysis setup allows for solution-phase photolysis to occur within a syringe using UVA LEDs, immediately prior to being introduced into the mass spectrometer via ESI. Gas-phase photofragmentation studies via laser-interfaced mass spectrometry of deprotonated riboflavin, [RFH], the dominant solution-phase species under the conditions of our study, are presented alongside the solution-phase photolysis. The results obtained illustrate the extent to which gas-phase photolysis methods can inform our understanding of the corresponding solution-phase photochemistry. We determine that the solution-phase photofragmentation observed for [RFH] closely mirrors the gas-phase photochemistry, with the m/z 241 ion being the only major condensed-phase photoproduct. Further gas-phase photoproducts are observed at m/z 255, 212, and 145. The value of exploring both the gas- and solution-phase photochemistry to characterize photochemical reactions is discussed.


2020 ◽  
Vol 20 (6) ◽  
pp. 3697-3711 ◽  
Author(s):  
Philipp G. Eger ◽  
Jan Schuladen ◽  
Nicolas Sobanski ◽  
Horst Fischer ◽  
Einar Karu ◽  
...  

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.


2018 ◽  
Author(s):  
James M. Mattila ◽  
Patrick Brophy ◽  
Jeffrey Kirkland ◽  
Samuel Hall ◽  
Kirk Ullmann ◽  
...  

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