Journal cover Journal topic
Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
Journal topic

Journal metrics

Journal metrics

  • IF value: 3.248 IF 3.248
  • IF 5-year value: 3.650 IF 5-year 3.650
  • CiteScore value: 3.37 CiteScore 3.37
  • SNIP value: 1.253 SNIP 1.253
  • SJR value: 1.869 SJR 1.869
  • IPP value: 3.29 IPP 3.29
  • h5-index value: 47 h5-index 47
  • Scimago H index value: 60 Scimago H index 60
Volume 11, issue 4 | Copyright
Atmos. Meas. Tech., 11, 1901-1920, 2018
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 05 Apr 2018

Research article | 05 Apr 2018

Measurement of formic acid, acetic acid and hydroxyacetaldehyde, hydrogen peroxide, and methyl peroxide in air by chemical ionization mass spectrometry: airborne method development

Victoria Treadaway1, Brian G. Heikes1, Ashley S. McNeill1,2, Indira K. C. Silwal3,4, and Daniel W. O'Sullivan3 Victoria Treadaway et al.
  • 1Graduate School of Oceanography, University of Rhode Island, Narragansett, RI 02882, USA
  • 2Department of Chemistry, University of Alabama, Tuscaloosa, AL 35401, USA
  • 3Chemistry Department, United States Naval Academy, Annapolis, MD 21402, USA
  • 4Forest Bioproducts Research Institute, University of Maine, Orono, ME 04469, USA

Abstract. A chemical ionization mass spectrometry (CIMS) method utilizing a reagent gas mixture of O2, CO2, and CH3I in N2 is described and optimized for quantitative gas-phase measurements of hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), formic acid (HCOOH), and the sum of acetic acid (CH3COOH) and hydroxyacetaldehyde (HOCH2CHO; also known as glycolaldehyde). The instrumentation and methodology were designed for airborne in situ field measurements. The CIMS quantification of formic acid, acetic acid, and hydroxyacetaldehyde used I cluster formation to produce and detect the ion clusters I(HCOOH), I(CH3COOH), and I(HOCH2CHO), respectively. The CIMS also produced and detected I clusters with hydrogen peroxide and methyl peroxide, I(H2O2) and I(CH3OOH), though the sensitivity was lower than with the O2 (CO2) and O2 ion clusters, respectively. For that reason, while the I peroxide clusters are presented, the focus is on the organic acids. Acetic acid and hydroxyacetaldehyde were found to yield equivalent CIMS responses. They are exact isobaric compounds and indistinguishable in the CIMS used. Consequently, their combined signal is referred to as the acetic acid equivalent sum. Within the resolution of the quadrupole used in the CIMS (1mz), ethanol and 1- and 2-propanol were potential isobaric interferences to the measurement of formic acid and the acetic acid equivalent sum, respectively. The CIMS response to ethanol was 3.3% that of formic acid and the response to either 1- or 2-propanol was 1% of the acetic acid response; therefore, the alcohols were not considered to be significant interferences to formic acid or the acetic acid equivalent sum. The multi-reagent ion system was successfully deployed during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) in 2014. The combination of FRAPPÉ and laboratory calibrations allowed for the post-mission quantification of formic acid and the acetic acid equivalent sum observed during the Deep Convective Clouds and Chemistry Experiment in 2012.

Publications Copernicus
Short summary
A multi-reagent ion chemical ionization mass spectrometer was developed to quantify formic acid, acetic acid and hydroxyacetaldehyde (referred to as acetic acid equivalent sum, AAES), hydrogen peroxide and methyl peroxide. This set-up was successfully deployed in the field during the 2014 Front Range Air Pollution and Photochemistry Exp. Laboratory and field work allowed the post-mission quantification of both formic acid and AAES sum during the 2012 Deep Convective Clouds and Chem. Exp.
A multi-reagent ion chemical ionization mass spectrometer was developed to quantify formic acid,...