No abstract

Abstract. We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to (i) characterize the VOC budget and (ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70 % and 95 % of annually emitted VOC carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2× larger source of nonmethane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half of the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC abundance (R2=0.36) and reactivity (R2=0.54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (∼ 60 %), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL : FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene + oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation.

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. Although hydrogen peroxide and methyl peroxide also form cluster ions with I-, the focus here 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 (1 m/z), 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 acetic 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.

Abstract. An ion-neutral chemical kinetic model is described and used to simulate the negative ion chemistry occurring within a mixed-reagent ion chemical ionization mass spectrometer (CIMS). The model objective was the establishment of a theoretical basis to understand ambient pressure (variable sample flow and reagent ion carrier gas flow rates), water vapor, ozone and oxides of nitrogen effects on ion cluster sensitivities for hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), formic acid (HFo) and acetic acid (HAc). The model development started with established atmospheric ion chemistry mechanisms, thermodynamic data and reaction rate coefficients. The chemical mechanism was augmented with additional reactions and their reaction rate coefficients specific to the analytes. Some existing reaction rate coefficients were modified to enable the model to match laboratory and field campaign determinations of ion cluster sensitivities as functions of CIMS sample flow rate and ambient humidity. Relative trends in predicted and observed sensitivities are compared as instrument specific factors preclude a direct calculation of instrument sensitivity as a function of sample pressure and humidity. Predicted sensitivity trends and experimental sensitivity trends suggested the model captured the reagent ion and cluster chemistry and reproduced trends in ion cluster sensitivity with sample flow and humidity observed with a CIMS instrument developed for atmospheric peroxide measurements (PCIMSs). The model was further used to investigate the potential for isobaric compounds as interferences in the measurement of the above species. For ambient O3 mixing ratios more than 50 times those of H2O2, O3−(H2O) was predicted to be a significant isobaric interference to the measurement of H2O2 using O2−(H2O2) at m∕z 66. O3 and NO give rise to species and cluster ions, CO3−(H2O) and NO3−(H2O), respectively, which interfere in the measurement of CH3OOH using O2−(CH3OOH) at m∕z 80. The CO3−(H2O) interference assumed one of its O atoms was 18O and present in the cluster in proportion to its natural abundance. The model results indicated monitoring water vapor mixing ratio, m∕z 78 for CO3−(H2O) and m∕z 98 for isotopic CO3−(H2O)2 can be used to determine when CO3−(H2O) interference is significant. Similarly, monitoring water vapor mixing ratio, m∕z 62 for NO3− and m∕z 98 for NO3−(H2O)2 can be used to determine when NO3−(H2O) interference is significant.

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 (1 m∕z), 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.