Measurement of Formic Acid, Acetic Acid and Hydroxyacetaldehyde

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Measurement of Formic Acid, Acetic Acid and Hydroxyacetaldehyde University of Rhode Island DigitalCommons@URI Graduate School of Oceanography Faculty Graduate School of Oceanography Publications 2018 Measurement of Formic Acid, Acetic Acid and Hydroxyacetaldehyde, Hydrogen Peroxide, and Methyl Peroxide in Air by Chemical Ionization Mass Spectrometry: Airborne Method Victoria Treadaway University of Rhode Island Brian G. Heike University of Rhode Island, [email protected] See next page for additional authors Creative Commons License This work is licensed under a Creative Commons Attribution 4.0 License. Follow this and additional works at: https://digitalcommons.uri.edu/gsofacpubs Citation/Publisher Attribution Treadaway, V., Heikes, B. G., McNeill, A. S., Silwal, I. K. C., and O'Sullivan, D. W.: Measurement of formic acid, acetic acid and hydroxyacetaldehyde, hydrogen peroxide, and methyl peroxide in air by chemical ionization mass spectrometry: airborne method development, Atmos. Meas. Tech., 11, 1901-1920, https://doi.org/10.5194/amt-11-1901-2018, 2018. This Article is brought to you for free and open access by the Graduate School of Oceanography at DigitalCommons@URI. It has been accepted for inclusion in Graduate School of Oceanography Faculty Publications by an authorized administrator of DigitalCommons@URI. For more information, please contact [email protected]. Authors Victoria Treadaway, Brian G. Heike, Ashley S. McNeill, Indira K. C. Silwal, and Daniel W. O'Sullivan This article is available at DigitalCommons@URI: https://digitalcommons.uri.edu/gsofacpubs/512 Atmos. Meas. Tech., 11, 1901–1920, 2018 https://doi.org/10.5194/amt-11-1901-2018 © Author(s) 2018. This work is distributed under the Creative Commons Attribution 4.0 License. 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 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 Correspondence: Victoria Treadaway ([email protected]) Received: 22 September 2017 – Discussion started: 4 October 2017 Revised: 5 January 2018 – Accepted: 1 February 2018 – Published: 5 April 2018 Abstract. A chemical ionization mass spectrometry (CIMS) ences to formic acid or the acetic acid equivalent sum. The method utilizing a reagent gas mixture of O2, CO2, and multi-reagent ion system was successfully deployed during CH3I in N2 is described and optimized for quantitative the Front Range Air Pollution and Photochemistry Éxperi- gas-phase measurements of hydrogen peroxide (H2O2), ment (FRAPPÉ) in 2014. The combination of FRAPPÉ and methyl peroxide (CH3OOH), formic acid (HCOOH), and laboratory calibrations allowed for the post-mission quantifi- the sum of acetic acid (CH3COOH) and hydroxyacetalde- cation of formic acid and the acetic acid equivalent sum ob- hyde (HOCH2CHO; also known as glycolaldehyde). The served during the Deep Convective Clouds and Chemistry instrumentation and methodology were designed for air- Experiment in 2012. borne in situ field measurements. The CIMS quantification of formic acid, acetic acid, and hydroxyacetaldehyde used I− cluster formation to produce and detect the ion clus- − − − ters I (HCOOH), I (CH3COOH), and I (HOCH2CHO), 1 Introduction respectively. The CIMS also produced and detected I− clus- − ters with hydrogen peroxide and methyl peroxide, I (H2O2) Formic acid (HCOOH, hereafter referred to as HFo), acetic − and I (CH3OOH), though the sensitivity was lower than acid (CH3COOH, hereafter referred to as HAc), and hy- − − with the O2 (CO2) and O2 ion clusters, respectively. For droxyacetaldehyde (HOCH2CHO, commonly referred to as that reason, while the I− peroxide clusters are presented, the glycolaldehyde, and hereafter abbreviated as GA) are oxy- focus is on the organic acids. Acetic acid and hydroxyac- genated volatile organic compounds (OVOCs) found in re- etaldehyde were found to yield equivalent CIMS responses. mote and urban environments in both gas and particle forms. They are exact isobaric compounds and indistinguishable in Primary emissions for both acids include vegetation, agricul- the CIMS used. Consequently, their combined signal is re- ture, biomass burning, and motor vehicle emissions (Khare ferred to as “the acetic acid equivalent sum”. Within the res- et al., 1999; Paulot et al., 2011). Secondary sources also olution of the quadrupole used in the CIMS (1 m=z), ethanol play a substantial role in the formation and distribution of and 1- and 2-propanol were potential isobaric interferences HFo and HAc and include photochemical production from to the measurement of formic acid and the acetic acid equiv- gaseous VOCs and OVOCs of biogenic and anthropogenic alent sum, respectively. The CIMS response to ethanol was origin, biomass burning, and primary and secondary organic 3.3 % that of formic acid and the response to either 1- or aerosols (Khare et al., 1999; Paulot et al., 2011). Both or- 2-propanol was 1 % of the acetic acid response; therefore, ganic acids are photochemically long lived (> 10 days with the alcohols were not considered to be significant interfer- respect to HO photooxidation) and their removal is primar- Published by Copernicus Publications on behalf of the European Geosciences Union. 1902 V. Treadaway et al.: Multi-ion CIMS organic acids and peroxides ily by dry and wet deposition at Earth’s surface (Paulot et al., rectly effects precipitation acidity (Khare et al., 1999; Paulot 2011). Away from Earth’s surface, these acids represent a rel- et al., 2011). Finally, both GA and HAc are participants in atively long-lived intermediate product in the oxidation of the formation and growth of organic aerosols and in aerosol organic matter. However, there is a scarcity of organic acid photochemical processing (Carlton et al., 2006; Fuzzi and measurements in the upper troposphere with which to com- Andreae, 2006; Lee et al., 2006; Perri et al., 2010; Yu, 2000). pare and assess photochemical and transport theory. Millet Airborne platforms provide one vehicle for instrumentation et al. (2015), Reiner et al. (1999), and Talbot et al. (1996) to measure these compounds throughout the depth of the tro- reported vertical profiles for HFo and HAc; however, only posphere (e.g., Le Breton et al., 2012; Lee et al., 1998; Millet Reiner et al. and Talbot et al. sampled above 7 km. In remote et al., 2015; Talbot et al., 1996) and this adds an additional environments, HFo and HAc are the primary acids establish- need for “fast” instruments, especially for situations in which ing the pH of cloud water and precipitation (Galloway et al., spatial–temporal scales are relatively small, such as in the 1982). HFo and HAc partitioning between gas and aqueous boundary layer or near convective clouds. phases is pH dependent. In the aqueous phase, both HFo In recent years there has been an increase in the number and HAc remain in the protonated form below their pKas of of atmospheric gas-phase species measured using chemical 3.75 and 4.76 (T D 298:15 K), respectively (Johnson et al., ionization mass spectrometry (CIMS) (Huey, 2007). The ma- 1996). As emission controls on anthropogenic NOx and SO2 jor advantages of CIMS include rapid response times with continue to decrease the contributions of these gases to pre- high sensitivity and selectivity (e.g., Bertram et al., 2011; cipitation acidity, the organic acids are expected to compose Crounse et al., 2006). Previous studies have successfully a larger fractional contribution to acidity in cloud water and measured gas-phase HFo and HAc via negative-ion-mode − − precipitation. CIMS using trifluoromethoxy anion (CF3O ), iodide (I ), − Hydroxyacetaldehyde (or GA) is formed by the HO oxi- or acetate (CH3COO ) as the reagent ion (e.g., Amelynck dation of biogenic VOCs such as isoprene and methyl vinyl et al., 2000; Le Breton et al., 2012; Brophy and Farmer, ketone (MVK) (Lee et al., 1998; Tuazon and Atkinson, 1989) 2015; Veres et al., 2008). Yuan et al. (2016) reported HFo C and by the HO oxidation of unsaturated anthropogenic VOCs and HAc using a H3O time-of-flight CIMS. Brophy and like ethene (Niki et al., 1981). GA has also been measured Farmer (2015) developed a dual reagent ion system with I− − in smoldering biomass burning plumes and can be up to used for HAc and CH3COO used for HFo, in which the 1 % of the gaseous carbon detected in fire emissions (John- reagent gases are added in an alternating sequence. However, son et al., 2013; Yokelson et al., 1997). Table S1 provides to our knowledge, to date only one group has reported results a summary of literature surface and aircraft measurements for both HFo and HAc using an I−CIMS (Lee et al., 2014). for GA in urban, biomass burning, biogenic, and mixed en- Proton-transfer-reaction mass spectrometry (PTR-MS) has C vironments. GA’s primary loss is by HO oxidation and wet been used to quantify HFo and HAc with H3O as the deposition (Bacher et al., 2001). The effective Henry’s Law reagent ion (e.g., Müller et al., 2014); Wisthaler reports the constant for GA (70 MhPa−1) is surprisingly large (Betterton sum of HAc and GA (Armin Wisthaler, personal communi- and Hoffmann, 1988) and an order of magnitude larger than cation, 2015) using this methodology. that for HAc (7.8 MhPa−1) at a temperature of 288 K (John- O’Sullivan et al. (2018) and Heikes et al. (2017) described son et al., 1996; results below). GA is more likely than HAc a CIMS instrument for the airborne measurement of perox- to be removed by precipitation during transport through deep ides called PCIMS. In the course of developing the PCIMS, convection based upon model work by Barth et al.
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