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2018 An Ion-Neutral Model to Investigate Chemical Ionization Mass Spectrometry Analysis of Atmospheric Molecules – Application to a Mixed Reagent Ion System for Hydroperoxides and Organic Acids Brian G. Heikes University of Rhode Island, [email protected]
Victoria Treadaway University of Rhode Island
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Citation/Publisher Attribution Heikes, B. G., Treadaway, V., McNeill, A. S., Silwal, I. K. C., and O'Sullivan, D. W.: An ion-neutral model to investigate chemical ionization mass spectrometry analysis of atmospheric molecules – application to a mixed reagent ion system for hydroperoxides and organic acids, Atmos. Meas. Tech., 11, 1851-1881, https://doi.org/10.5194/amt-11-1851-2018, 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 Brian G. Heikes, Victoria Treadaway, Ashley S. McNeill, Indira K. C. Silwal, and Daniel W. O'Sullivan
This article is available at DigitalCommons@URI: https://digitalcommons.uri.edu/gsofacpubs/513 Atmos. Meas. Tech., 11, 1851–1881, 2018 https://doi.org/10.5194/amt-11-1851-2018 © Author(s) 2018. This work is distributed under the Creative Commons Attribution 4.0 License.
An ion-neutral model to investigate chemical ionization mass spectrometry analysis of atmospheric molecules – application to a mixed reagent ion system for hydroperoxides and organic acids
Brian G. Heikes1, Victoria Treadaway1, 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, The 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 04469, USA
Correspondence: Brian G. Heikes ([email protected])
Received: 4 August 2017 – Discussion started: 20 September 2017 Revised: 19 January 2018 – Accepted: 5 February 2018 – Published: 4 April 2018
− Abstract. An ion-neutral chemical kinetic model is de- O (H2O) was predicted to be a significant isobaric inter- 3 − scribed and used to simulate the negative ion chemistry oc- ference to the measurement of H2O2 using O2 (H2O2) at curring within a mixed-reagent ion chemical ionization mass m/z 66. O3 and NO give rise to species and cluster ions, − − spectrometer (CIMS). The model objective was the establish- CO (H2O) and NO (H2O), respectively, which interfere 3 3 − ment of a theoretical basis to understand ambient pressure in the measurement of CH3OOH using O (CH3OOH) at − 2 (variable sample flow and reagent ion carrier gas flow rates), m/z 80. The CO3 (H2O) interference assumed one of its O water vapor, ozone and oxides of nitrogen effects on ion clus- atoms was 18O and present in the cluster in proportion to ter sensitivities for hydrogen peroxide (H2O2), methyl per- its natural abundance. The model results indicated monitor- − oxide (CH3OOH), formic acid (HFo) and acetic acid (HAc). ing water vapor mixing ratio, m/z 78 for CO (H2O) and − 3 The model development started with established atmospheric m/z 98 for isotopic CO (H2O)2 can be used to determine − 3 ion chemistry mechanisms, thermodynamic data and reaction when CO3 (H2O) interference is significant. Similarly, moni- rate coefficients. The chemical mechanism was augmented toring water vapor mixing ratio, m/z 62 for NO− and m/z 98 − 3 − with additional reactions and their reaction rate coefficients for NO3 (H2O)2 can be used to determine when NO3 (H2O) specific to the analytes. Some existing reaction rate coeffi- interference is significant. cients were modified to enable the model to match laboratory and field campaign determinations of ion cluster sensitivi- ties as functions of CIMS sample flow rate and ambient hu- midity. Relative trends in predicted and observed sensitivities 1 Introduction are compared as instrument specific factors preclude a direct calculation of instrument sensitivity as a function of sample Atmospheric measurements of hydrogen peroxide (H2O2), pressure and humidity. Predicted sensitivity trends and ex- methyl peroxide (CH3OOH), formic acid (hereafter referred perimental sensitivity trends suggested the model captured to as HFo) and acetic acid (hereafter referred to as HAc) the reagent ion and cluster chemistry and reproduced trends have evolved over the past half century. Current state-of-the- in ion cluster sensitivity with sample flow and humidity ob- art measurements use chemical ionization mass spectrome- served with a CIMS instrument developed for atmospheric try (e.g., Crounse et al., 2006; de Gouw and Warneke, 2007; peroxide measurements (PCIMSs). The model was further Veres et al., 2008; St. Clair et al., 2010; Le Breton et al., used to investigate the potential for isobaric compounds as 2012; Lee et al., 2014; Baasandorj et al., 2015; O’Sullivan interferences in the measurement of the above species. For et al., 2018; Treadaway et al., 2018) with a variety of reagent + − − − h i − −h i ambient O3 mixing ratios more than 50 times those of H2O2, ions (e.g., H3O ,O2 , CF3O ,I , CH3C O O ,O2 CO2 ).
Published by Copernicus Publications on behalf of the European Geosciences Union. 1852 B. G. Heikes et al.: TS6 PCIMS instrument ion-chemistry model
O’Sullivan et al. (2018) and Treadaway et al. (2018) have Ambient pressure changes can also lead to decreasing or presented a hybrid reagent ion instrument for the simultane- increasing sensitivity with an increase in sample pressure ous measurement of the peroxides and organic acids. Here (flow) . The objective of this paper is to present a model an ion-neutral chemical kinetic model is described and used chemical mechanism which provides a theoretical basis to to simulate the negative ion chemistry occurring within their investigate the influences of ambient pressure (variable sam- mixed-reagent gas chemical ionization mass spectrometer ple flow and reagent ion carrier gas flow rates), water vapor (PCIMS). The ”P” is derived from the instrument’s original and other trace gases: ozone (O3), nitric oxide (NO), nitro- configuration to measure H2O2 and CH3OOH (O’Sullivan et gen dioxide (NO2) and nitric acid (HNO3) on ion cluster sen- al., 2018), and which was later modified to quantify HFo and sitivities for H2O2, CH3OOH, HFo and HAc. The model is HAc (Treadaway, 2015; Treadaway et al., 2018). extensible to simulating the negative ion chemistry of other The PCIMS instrument and basic ion cluster schemes are reagent gas, ion source and reaction cell or drift-tube sys- described in O’Sullivan et al. (2018), Treadaway (2015) and tems. Treadaway et al. (2018). Serendipity led to the use of a mixed reagent gas stream composed of nitrogen (N2), oxygen (O2), 2 Methods carbon dioxide (CO2) and iodomethane (CH3I).O2 and − − − CO2 reagent gases provided O2 ,O2 (O2) and O2 (CO2) as − 2.1 PCIMS instrument reagent ions. CH3I reagent gas yielded iodide ions I . The PCIMS instrument was specifically designed to be mounted The physical PCIMS instrument is described in O’Sullivan and utilized from an aircraft and was flown on the NCAR et al. (2018), Treadaway (2015) and Treadaway et al. (2018). HIAPER (UCAR/NCAR-EOL, 2005) aircraft in the Deep A physical description of the instrument and calibration Convective Clouds and Chemistry experiment (DC3; Barth schemes are presented in the Appendix. The instrument flow et al., 2015) and on the NCAR C-130 (UCAR/NCAR-EOL, and electronic configuration described in the Appendix was 1994) aircraft in the Front Range Air Pollution and Photo- used throughout the field and laboratory work reported here. chemistry Experiment (FRAPPE; https://www2.acom.ucar. The PCIMS m/z range was 1–500 m/z and the mass resolu- edu/frappe). In these programs, a fixed area critical orifice tion was 1.0 m/z. The main component effecting ion clus- was used on the sample inlet to the PCIMS. Consequently, ter transmission through the system was the collision dis- the air sample flow rate into the instrument varied with am- sociation chamber (CDC) consisting of an entrance plate bient sample pressure and analyte sensitivity (defined as the and octopole ion guide. The CDC plate DC voltage and the cluster ion counts per second per analyte reaction cell mix- octopole DC and RF voltages were adjusted to maximize −1 ing ratio, e.g., cps ppb ), varied with ambient pressure. As the transmission of the hydroperoxide analyte cluster ions documented for many atmospheric CIMS instruments (e.g., − − O2 (CO2)(H2O2) and O2 (CH3OOH) and to reduce the sig- Slusher et al., 2004; Crounse et al., 2006; St. Clair et al., nal from other ions near their respective masses. To estimate 2010; Le Breton et al., 2012; Lee et al., 2014; Baasandorj et the “declustering” energy employed, an analysis of the ther- al., 2015), analyte sensitivity was dependent upon the reac- modynamics of the following hydration reactions: tion cell water vapor mixing ratio. The humidity and pressure sensitivity dependencies were complex and explored in the − + − ; = − O2 (H2O)n−1 H2OO2 (H2O)n n 1 5, laboratory to improve calibration. As will be shown below − − CO (H2O) − + H2OCO (H2O) ; n = 1 − 3, within the discussion section, depending upon the reagent 3 n 1 3 n − + − ; = − ion–analyte pair, the effect of water vapor can lead to: NO3 (H2O)n−1 H2ONO3 (H2O)n n 1 2,
1. a relative constant sensitivity as water vapor mixing ra- and tios increase until near maximum water vapor mixing I−(H O) + H OI−(H O) ; n = 1 − 4, ratios are encountered after which the sensitivity de- 2 n−1 2 2 n creases with increasing water vapor; and the PCIMS signals of the respective hydrates was car- ried out. There was an absence of signals for O−(H O) , 2. sensitivity increases as water vapor mixing ratio in- 2 2 n>3 CO−(H O) and I−(H O) clusters. The absence of creases; 3 2 n>2 2 n>1 these clusters suggested a CDC “declustering” enthalpy cut −1 3. sensitivity decreases as water vapor mixing ratio in- off at −50 kJ mol or a CDC “declustering” Gibbs en- −1 creases; and ergy of −20 kJ mol . The thermodynamic data used in this analysis were from NIST Chemistry WebBook SRD69 4. “parabolic” response in which the sensitivity to an ion– (Bartmess, 2016). − analyte cluster is low at low water vapor mixing ratio, PCIMS uses a mixed reagent ion chemistry: O2 , − − passes through a maximum sensitivity at an intermedi- O2 (CO2) and I to produce cluster ions with H2O2 − − − ate water vapor mixing ratio, and is low again at high [O (H2O2),O (CO2)(H2O2),I (H2O2) at masses 66, 2 2 − water vapor mixing ratio. 110 and 161, respectively], with CH3OOH [O2 (CH3OOH),
Atmos. Meas. Tech., 11, 1851–1881, 2018 www.atmos-meas-tech.net/11/1851/2018/ B. G. Heikes et al.: TS6 PCIMS instrument ion-chemistry model 1853 mass 80], with HFo [I− (HFo), mass 173] and HAc (5–10 slpm) and humidified lines (0–5 slpm) and the total [I− (HAc), mass 187]. There is a weaker signal for flow was maintained at 10 slpm. The water concentration in − I (CH3OOH) at mass 175 but it is not considered in the the humidified line is controlled with two gas washing bot- model. tles and a gas-water equilibration coil immersed in a water In flight, ambient air was sampled through a heated probe bath held at either 15 or 25 ◦C. At the latter bath tempera- held at 30 ◦C in DC3 and 70 ◦C in FRAPPE. The higher tem- ture, it was necessary to reset the room temperature from 22 perature in FRAPPE was used to partially alleviate an inlet to 30 ◦C to prevent condensation in the line. For some ex- contamination issue. Sample air is passed from the inlet to periments, gas standard additions were performed with an the instrument using heated PFA® Teflon tubing. All “wet- external Henry’s Law type equilibration coil with concur- ted” surfaces from the probe to the physical instrument are rent aqueous flow at 0.4 mL min−1, air flow at 0.4 slpm, gas PFA® Teflon. The inlet system is pumped by the instrument’s and aqueous flows are separated at the end of the coil us- vacuum system and by a second scroll pump (Varian model ing a cyclone separator, and the coil/cyclone is immersed IDP-3) to increase sample airflow though the inlet tubing, in a water bath held at 15 ◦C. The Henry’s Law system was therefore improving response time and ameliorating poten- plumbed to the carrier air stream after the humidification line. tial wall artifacts in H2O2, CH3OOH, HFo and HAc. Stan- A needle valve was used to simulate lower ambient pressures dard additions of hydroperoxides were performed in DC3 (Fig. A2a) as in flight. The aircraft standard addition system and hydroperoxide and organic acid standard additions were was also used and this remained plumbed downstream of the performed in FRAPPE. The gas standards were added before laboratory air pressure control system. Air pressures between a selectable entrance to two traps in series (Carulite-200®, 120 and 1013 hPa were sampled (nominally set at 120, 180, Carus Corp., Peru, IL; NaOH on fiberglass wool). There was 300, 600 and 1013 hPa). By changing the proportion of air a constant flow of standard gas to within 0.3 m of the inlet flow through the dry (10, 9, 8, 7, 6 and 5 slpm) and humid- and a “draw-back” line was used to divert the standard and ified lines (0, 1, 2, 3, 4, and 5 slpm) and the inlet pressure, an equal amount of sample air to waste under normal con- it was possible to alter the reaction cell water vapor mixing ditions (Fig. A2b). A 2-way valve on the “draw-back” line ratio from 30 to 20 000 ppm. of the syringe addition system and a 3-way valve near the instrument inlet (Fig. A2b) were used to select between one 2.2 Ion-neutral chemical mechanism of four modes: (1) the sample air, (2) sample air with gas standard addition, (3) sample air passed through the traps as The chemical mechanism is guided by the ion-neutral reac- a field blank or (4) sample air with gas standards added and tion suites and kinetic summaries of Albritton (1978), Huer- passed through the traps to evaluate trap efficiency. In this tas et al. (1978), Ikezoe et al. (1987), Turunen et al. (1996), way instrument calibration and trap efficiency were moni- Kazil (2002), Popov (2010) and Kovács et al. (2016) devel- tored. oped to simulate ion-neutral chemistry of the atmosphere. H2O2, CH3OOH and CD3OOH (trideuterated methyl per- Necessary modifications and extensions of the chemical oxide) gas standard additions are available for research mechanisms to fit the PCIMS sensitivities are described here flights 6–22 in DC3. H2O2 and HFo standard additions are and in more detail within the Supplement. reported for all 15 research flights in FRAPPE. However, Some trace components of ambient air can compete for the in FRAPPE, the instrument experienced severe vibration reagent ions and ion-neutral clusters effecting the yield (sen- in flight, which caused “chatter” in the MFCs (mass flow sitivity) of the analyte ion clusters of interest as well as form- controllers), and there was a significant contaminant in the ing isobaric interfering ion or ion clusters. Analyte ion clus- hanger. Consequently, CH3OOH calibrations were reported ters and identified potential interfering ion species at specific for the last 11 flights after the MFC mounts were reconfig- m/z ratios are listed in Table 1. Also listed are primary ion ured and “chatter” was greatly reduced. HAc standard ad- cluster m/z ratios used to assess potential isobaric interfer- − ditions were only available for a portion of these FRAPPE ences. For example, m/z 78 is used to monitor CO3 (H2O), flights as the contamination problem was only minimized on which in turn is used to estimate the potential interference at − longer flights or after high altitude runs. The standard addi- m/z 80 from CO3 (H2O) should one of its four O atoms be tions used here were further screened to ensure each standard a mass 18 stable isotope of oxygen, 18O, and present at its addition cycle, (ambient air, ambient air with gas standards natural abundance of 0.204 %. added, ambient air), was completed at constant pressure (al- Time-dependent concentrations of 73 species (neutrals, titude). ions and ion clusters), listed in Appendix Table A1, are pre- The laboratory calibration set up is described fully in dicted in time according to the 209 bi- and ter-molecular Treadaway (2015) and only briefly here (block schematic reactions presented in Appendix Table A2. For clarity, ana- shown in Fig. A2a). A pure-air generator (Model 737-10A, lyte cluster ion formation reactions are re-listed in Table A3. Aadco Instruments Inc., Cleves, OH) supplied the carrier Potential isobaric interference ion cluster formation reaction ◦ air stream at 10 slpm (standard liters per minute, Tref =0 C, sequences are additionally listed in Table A4 for clarity. A Pref = 1013.25 hPa). This air stream was split between dry set of 72 ordinary differential equations was solved using www.atmos-meas-tech.net/11/1851/2018/ Atmos. Meas. Tech., 11, 1851–1881, 2018 1854 B. G. Heikes et al.: TS6 PCIMS instrument ion-chemistry model
Table 1. PCIMS m/z for species clusters of interest and potential (Bartmess, 2016). Generally available neutral, ion and ion isobaric interfering ions or ion clusters at the mass resolution of the cluster formation enthalpy, entropy and Gibb’s formation − quadrupole mass selector. Bold font indicates a primary PCIMS an- energy for the O − O2 − CO2 − H2O− hydroperoxide 18 2 alyte ion cluster mass; “ O of” indicates one of the ion cluster’s system are listed in Table A5 in the Appendix. Reaction oxygen atoms is a mass 18 isotope of oxygen; in CD3OOH the D enthalpy, reaction entropy and Gibb’s reaction energies for represents deuterium atoms; EtOH refers to ethanol; PrOH refers this system are listed in Table A6 in the Appendix. Notes to 1-propanol; 2-PrOH refers to 2-propanol; CH (OH) refers to 2 2 on the development of the thermodynamic Tables A5 and methane-diol; MeFo refers to methyl formate; and GA refers to hy- droxy acetaldehyde (a.k.a. glycolaldehyde). A6 are given in the Supplement Sect. S1.1. As called out below and in the Supplement, care is required in applying K = kforward as the implied reaction system may not m/z Ion or ion-neutral cluster eq kreverse − 18 − represent a simple concerted reaction pair in equilibrium but 50 O (H2O), O of O 2 − 3 involve a reaction sequence in steady-state. For several of 60 CO3 − 18 − the ion-hydrate cluster reactions: 62 NO3 , O of CO3 18 − − 18 − 66 O2− (H2O2), O of NO2 (H2O), O3 (H2O), O of O2 (O2) − − − X (H2O)n−1 + H2O + M ↔ X (H2O)n + M 76 O2 (CO2) − 18 − 78 CO (H O), O of O (CO ) k o 3 2 2 2 hydration {G /R/To} − 18 − Keq = = e rxn , 80 O2− (CH3OOH), NO3 (H2O), O of CO3 (H2O), k − 18 − − dehydration NO (H2O2), O of O (HFo), O (CH2(OH)2) −2 2 2 83 O2 (CD3OOH) neither the forward termolecular hydration rate constant 110 O2− (CO2)(H2O2) − 18 (khydration) nor the bimolecular dehydration rate constant 147 I (H2 O) − − 18 16 (kdehydration) is known. In this case, rate coefficients are es- 161 I (H2O2), I ( O O) 173 I−(HFo), I−(EtOH), I−(C18O16O) timated from the observation that a strong correlation ex- − − − 175 I (CH3OOH), I (CH2(OH)2),I (O3) ists between the log of kdehydration and the Gibbs energy of − − − − − o 187 I (HAc), I (MeFo), I (PrOH), I (2-PrOH), I (GA) the hydration reaction (Grxn). The correlation is shown in Fig. 1a. Known dehydration rate coefficients include those that are experimentally determined by direct measurement the ode23t solver (MatLab version R2016b, The MathWorks, of kdehydration and those that are estimated from the hydration − Inc.) with relative tolerance equal to 3 × 10 9 and the abso- equilibrium constant and a measured khydration. For the cases − lute tolerance equal to 3 × 10 12. in which neither khydration or kdehydration is known, kdehydration o is first estimated using 1Grxn as its predictor (i.e., the lin- 2.3 Reaction rate coefficients ear regression model “fit” in Fig. 1a) and khydration is sub- sequently estimated from the predicted kdehydration value and Reaction rate coefficients are taken from Popov (2010), Keq. Figure 1b shows known khydrationand estimated khydration Kazil (2002), Ikezoe et al. (1987), Kawamoto and o plotted as a function of Grxn. Note further that, with only a Ogawa (1986), Fahey et al. (1982), Albritton (1978), few exceptions, individual khydration rates fall within a factor Huertas et al. (1978), Fehsenfeld and Fergusson (1974), of two of the mean value (dashed green line) and are near Adams et al. (1970), Fehsenfeld et al. (1969, 1967) and the collision limit. A factor of two falls within the accepted −1 references therein. Reaction rate coefficient units are s , uncertainty estimated for the reaction rate coefficients. The 3 −1 −1 6 −2 −1 cm molec s , and cm molec s for uni-, bi- and uncertainties in ion-molecule reaction rate coefficients as re- ter-molecular reactions, respectively. Equilibrium constants ported by their original authors are included in the summary determined using reaction Gibbs energy, have been converted by Ikezoe et al. (1987). Typically, reaction rate coefficient appropriately assuming (ideal gas behavior, Tref = 298.15 K, uncertainty is reported to be a factor of two (e.g., Albritton, 25 −3 Pref = 1013.25 hPa and Nref = 2.46 × 10 molec m ). 1978; Fahey et al., 1982; Ikezoe et al., 1987). Although for a Most of the reaction rate coefficients were experimentally few reactions, “best” reaction rate coefficient uncertainties of determined and a few were theoretically estimated (e.g., ±20 % can be found (e.g., Ikezoe et al., 1987). Here a factor Kazil, 2002; Iyer et al., 2016). However, some of the rate of two is taken as the uncertainty in the reaction rate coeffi- constants listed in the above compilations were simply cients. Additional notes on the development of reaction rate presumed (e.g., Mohnen, 1972; Huertas et al., 1978) and coefficients are given in Sect. 1.2–1.4 of the Supplement. these presumptions have carried forward into later works. The following generic equilibrium reaction sequences, af- Several rate coefficients were estimated from the Gibb’s ter, e.g., Crounse et al. (2006) and Le Breton et al. (2012), o − reaction energy, Grxn, or equilibrium constant, Keq, with are used to describe negative ion, X , cluster formation with either a measured forward or reverse reaction rate co- an analyte, A, representing H2O2, CH3OOH, HFo, and HAc: efficient following Albritton (1978), i.e., K = kfor and eq krev o − − {G /(RTo)} X + H O + M ↔ X (H O) + M (R1) Keq = e rxn . The majority of Gibbs reaction energies 2 2 are taken directly from the NIST Chemistry WebBook X− + A + M ↔ X− (A) + M (R2)
Atmos. Meas. Tech., 11, 1851–1881, 2018 www.atmos-meas-tech.net/11/1851/2018/ B. G. Heikes et al.: TS6 PCIMS instrument ion-chemistry model 1855
1.0E-27 (b) (a)
1 1E-11 -
1
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c ,
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r 1E-19 o kf d m y r h kb e Average forward t e
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e 1E-21 t w r s kb-est kf-est o u l F C 1E-23 1.0E-29 0 102030405060708090 0 20 40 60 80 100 120 Gibbs energy of cluster ion hydra on, n = 1, 2, 3; kJ mol-1 Gibbs energy of hydra on, n = 1, 2, or 3; kJ mol-1
o Figure 1. Ion cluster dehydration (a) and hydration (b) reaction rate coefficients plotted as a function of the Gibbs reaction energy (Grxn) − − − − − − − − = for I ,O2 ,O3 , CO3 , HO , NO , NO2 and NO3 ions for n 1–3 water molecules. Solid circles are reported rate coefficients from the o literature (see text) and open circles are estimates based upon linear regression of ln(kdehydration) versus Grxn or khydration = kdehydration × Keq.
− − X (H2O) + A ↔ X (A) + H2O (R3) and reactions like Reaction (R3f) are slow. Reactions (R1)–(R3) correspond to our Reactions (22)–(45). Assumption set B: product kR3r[X − (A)][H2O] As discussed below, we added poly-hydrate “switching” type becomes progressively larger than the sum of − reactions: kR2f[M][X−] and kR3fKR1[X ][H2O] as [H2O] increases. − − X (H2O)n + A ↔ X (A)(H2O)n−1 + H2O (R4) − For the most part, our ion–analyte cluster reaction kinetics to account for observed higher order humidity effects on O2 , are unstudied. The ion hydration kinetics of Reaction (R1) − − − O2 CO2 and I hydroperoxide and organic acid sensitiv- are discussed above. Measured reaction rate coefficients were ity. This simple system with a variety of reaction rate co- − − − available for H2O2 clustering with NO2 , NO3 , Cl and efficients can yield a suite of sensitivity responses to water − HSO4 (Böhringer et al., 1984). Iyer et al. (2016) using ab vapor. initio methods estimated reaction rate coefficients and bind- ing energies for I− with HFo and HAc. They also calculated – Case 1: sensitivity independent of water. − binding energies for I reactions with H2O2 and CH3OOH Assumptions, water vapor does not deplete the reagent − (Siddharth Iyer, personal communication, 2017). The cal- ion concentration and the product kR2f[M][X ] is much − − − culated binding energies for I (HFo),I (HAc),I (H2O2) larger than kR3fKR1[H2O] over the range of [H2O] en- − −1 and I (CH3OOH) were 100, 73, 70 and 60 kJ mol , re- countered. spectively. Iyer et al. predicted sensitivities for the Lee et – Case 2: sensitivity increases with water vapor mixing al. (2014) instrument using the calculated binding energies ratio. and measured sensitivities. We have normalized these to I− (HFo) and the predicted relative sensitivities were 1.000, Assumptions, water vapor does not deplete the reagent 0.034, 0.007 and 0.001 for I− (HFo),I− (HAc),I− (H O ) ion concentration and the product k [M][X−] is 2 2 R2f and I− (CH OOH), respectively. These were consistent with smaller than k K [X−][H O] over the range of 3 R3f R1 2 the observations of O’Sullivan et al. (2018) in which they [H2O] encountered. − − noted observing I (H2O2) and sometimes I (CH3OOH) – Case 3: sensitivity decreases with water vapor mixing clusters with the PCIMS instrument. They were further- ratio. more, consistent with Treadaway et al. (2018) in which they observed a weak standard addition calibration signal Assumption set A: water vapor depletes the reagent − ion concentration via Reaction (R1) and successive for I (CH3OOH) during FRAPPE and in the laboratory in hydration reactions represented by: preparation for FRAPPE. At the constant reaction cell instrument pressure of 22 hPa, − − X (H2O)m−1 + H2O + M ↔ X (H2O)m + M (R1’) the forward rate coefficient for Reaction (R2) was taken to be www.atmos-meas-tech.net/11/1851/2018/ Atmos. Meas. Tech., 11, 1851–1881, 2018 1856 B. G. Heikes et al.: TS6 PCIMS instrument ion-chemistry model
180 70 1 - -dGw, kJ mol-1 l (a) o -dG, kJ mol-1 (b)
160 m 1
-1
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2 k o R = 9.13E-01 -dG, est -dGhp, est , y m
140 g J r
k -dGw, est
e , 50 n y -1 E
g Linear (-dGw, kJ mol ) 120 r s e Linear (-dGhp, kJ mol-1) b n b i e
100 G 40
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y = 1.97E-01x - 2.32E+02 c t e 60 2 i v R = 9.65E-01 w S a
20 g 40 e e v N a g
20 e 10 N
0 1200 1300 1400 1500 1600 1700 0 Negative Gibbs Rxn energy of protona on, kJ mol-1 1200 1300 1400 1500 1600 1700 Nega ve protona on Rxn Gibbs energy, kJ mol-1
− o Figure 2. Relationship between the negative ion-protonation reaction Gibbs energy, 1GR4, and (a) negative ion-hydration reaction Gibbs − o − o energy, 1GR1, and ion-H2O2 cluster reaction Gibbs energy, 1GR2, or (b) negative H2O and H2O2 switching reaction Gibbs energy, − o = 1GR3. Reactions (R1)–(R4) refer to reactions introduced in the text with A H2O2. Filled symbols denote measured values and open symbols indicate estimated values. The lines indicate least square linear regression fits with the regression constants and coefficient of determination given in the respective boxes. The use of negative values of the Gibbs energy of reaction follows NIST (Bartmess, 2016) nomenclature.
o o constant and the reaction and its rate coefficient were given as the same regardless of whether 1HR5 or 1GR5 was used to o o o a pseudo-bimolecular reaction with an initial reaction rate co- predict 1GR1 or 1GR2 and subsequently 1GR3. As noted efficient of 3 × 10−9, which is near the bi-molecular collision in the Supplement, there is some question as to whether − limits calculated by Kazil (2002) and Iyer et al. (2016). This O2 (CO2)(H2O) follows a simple reaction pair or involves a reaction rate coefficient was presumed for Reaction (R3), as more complex set of reactions at steady state and a linear pre- o well, although in the literature switching reaction rate coeffi- diction of 1GR3 could be an oversimplification and a source cients on the order of 10−10 are also used as estimates. of error for reaction rate constants involving this species. The reverse reaction coefficient of Reaction (R2) is esti- The kinetics and equilibrium constants for CH3OOH ion mated using the assumed forward rate constant and the equi- cluster formation are more speculative. Cappa et al. (2001) o o librium constant for Reaction (R2). As noted above, reaction using ab initio methods have estimated 1HR2 and 1GR2 − − − −1 Gibbs energies and equilibrium constants are available for for cluster formation with CO3 , 69 and 34 kJ mol , re- o o − Reaction (R1) (Bartmess, 2016). A more limited set of Gibbs spectively, and 1HR3 and 1GR3 for Reaction (R3), 17 energies and equilibrium constants are available for Reac- and −9 kJ mol−1, respectively. Siddharth Iyer (personal com- tion (R2) with H2O2 as the analyte (Böhringer et al., 1984; munication, 2016) estimated the CH3OOH binding energy Cappa and Elrod, 2001; Messer et al., 2000; O’Sullivan et with I− is −60 kJ mol−1. Messer et al. (2000) also us- al., 2018). Following Böhringer, we used known reaction en- ing ab initio methods examined the kinetics and energet- o o − thalpies, 1HR5, or reaction Gibbs energies, 1GR5, of the ion ics of H2O2 and CH3OOH cluster ion formation with F . protonation reaction (Reaction R5), They reported theoretical collision-limit rate coefficients of 1.42 × 10−9 and 1.47 × 10−9, respectively, for reactions with − + + ↔ − X H XH (R5) F (H2O)3. Their theoretical rate coefficients were bracketed by their experimental determined rates of 0.96–1.92 × 10−9. as linear predictors of the reaction Gibbs energy for Re- The F−(H O) ion was the predominant reagent ion under o o 2 3 actions (R1) and (R2), 1GR1 and 1GR2, (and therefore their experimental humidity conditions that gave rise to an = − = − the equilibrium constant) with A H2O2 and X O2 , ion-peroxide signal. Messer et al. further stated the rate of − − − O2 (CO2) or I . Figure 2a illustrates the linear relation- reaction was relatively unchanged for F hydration numbers o o o ships between 1GR5 with 1GR1 for H2O, and with 1GR2 less than six. Payzant and Kebarle (1972), Fehsenfeld and for H2O2. Figure 2b shows the linear relationship between Ferguson (1974) and Fahey et al. (1982) discussed reaction 1Go and 1Go , where 1Go = 1Go − 1Go . Figure 2 − R5 R3 R3 R2 R1 rates of O2 with variable numbers of water molecules at- is plotted with A = H2O2 as introduced in Reactions (R2)– − tached and indicated they varied only slightly with different (R4). The predicted equilibrium constants, KR2, for O2 , extents of hydration. We have therefore assumed the reac- − − 16 7 7 − O (CO2) and I are 3.2 × 10 , 3.5 × 10 and 1.4 × 10 2 tion rate coefficients for hydrated O2 ions with H2O2 and (atm−1), respectively. The coefficients of determination were
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® CH3OOH do not vary significantly with hydration. The for- 2130 Electrostatic Eliminator ) generated on the order ward rate constants for Reactions (R2), (R3) and (R4) are of 1014 ion pairs per second. set at near the collision rate for H2O2 and CH3OOH. As a caveat, we note some switching reaction rate coefficients for 4. Ion and neutral molecule concentrations varied along the flow direction and were radially uniform in the ion less tightly bound neutral species, e.g., O2, CO2,H2O, are reported to be on the order of 10−10. source tube and reaction cell. Water vapor is commonly added to the CH3I reagent gas − 5. Gas fluid flow in the ion source tube and in the reaction stream in I based CIMS instruments because it enhances cell followed plug-flow. sensitivity for some analytes (e.g., Slusher et al., 2004; Le Breton et al., 2012). Whether this is because H2O is a bet- 6. The reagent gas stream and ambient air stream were ter third body energy carrier, such as in Reaction (R2), or mixed instantaneously and uniformly at the point of adds a switching reaction (Reaction R3) to the instrument’s contact. development of an I− (A) cluster ion is not clear, although 7. Ion clusters containing N2,O2, and CO2 as neutrals discussions point to the latter. Per Iyer et al. (2016), the Re- − were not considered with the exceptions of O (CO2) action (R2) forward reaction rate coefficient is initially set at − 2 the collision limit for HFo and HAc. The forward reaction and O2 (O2). rate coefficients for these two compounds in Reaction (R3) 8. Wall effects on negative ions, neutral species and het- were initially set at the collision limit. The hydration equi- erogeneous chemistry were ignored. The first assump- librium constants for I− are such that under our laboratory − − tion is supported by the fact the ion source tube and re- and field experimental conditions, I and I (H2O) domi- − − action cell walls have a 2 V bias applied. nate over I (H2O)n>1 ions. Even so at the highest humidities studied it was necessary to include Reaction (R4) for n = 2, 9. The negative ion positive ion recombination was param- + but inclusion of Reaction (R4) with n > 2 was unnecessary eterized using a single pseudo positive ion, “N2 ”, that even when the Reaction (R4) reaction rate coefficient was set reacts with each negative ion and whose rate constant at the collision limit. followed Kazil (2002) and was tracked through: Last, Iyer et al. (2016) examined the probability of col- k=6x10−8(300/T )+1.25×10−25[M](300/T ) lisional stabilization of HFo (atom number 5) compared N+ + X− −→ to maximum sensitivity molecules (atom number > 8) and 2 i neutral products, (157i) found the former gave sensitivities dependent on reaction cell pressure, whereas, the latter were independent of pressure. Our analytes have between four and six atoms and our use of where, 157i indicated the reaction was included for each collision limit reaction rate coefficients could have resulted of the negative ion species. in an over prediction of the rates of I− cluster formation. 2.5 Initial concentrations 2.4 Model assumptions The initial reagent gas mixture was composed of N2,O2, Individual model runs are performed in two stages. The first CO2 and CH3I in proportions that vary with sample air pres- simulated the chemistry of the ion source region (alpha emit- sure and sample-air flow rate. The total flow rate through ter, and reagent ion gas mixture). The product ion outflow the reaction cell was constant at 4.68 slpm (standard liters of the source was then instantaneously mixed with the sam- ◦ per minute; Tref = 0 C, Pref = 1013.25 hPa). The ambient air ple air stream and the ion-neutral chemistry of the reaction sample flow rate varied (range 0.3 to 3 slpm) with ambient cell was simulated second. The following assumptions were pressure (range 120 to 1013.25 hPa) as did the N2 flow rate made: through the ion-source tube (range 2.1 to 4.3 slpm). Reagent gas concentrations in the ion-source tube varied accordingly 1. Alpha particle emission was uniform along the ion and their initial concentrations for different sample pressures source tube length. and flow conditions are listed in Table 2. Six representative 2. The ions directly generated by the alpha particles pass- pressures are shown, which span the range of pressures en- − ing through > 99 % N2 gas consisted solely of e and countered in the DC3 and FRAPPE airborne field campaigns + and in the laboratory work. The ion source tube and reac- N2 ions; the mechanism included several negative ions + tion cell temperature and pressure were taken to be 25 ◦C and N2 is the only positive ion considered. and 22 hPa, respectively. The model chemical system was 3. The energy of a 210Po alpha particle is 5.3 MeV; the then integrated in time for the length of the gas transit time + − formation enthalpy of a N2 and e ion pair from N2 through the ion source tube. gas is 34 eV; thus, as a zeroth-order estimate, a 20 mCi Ambient air was then mixed with the reagent ion stream. 210Po alpha source (the stated activity of the NRD P- Ambient air, for the purpose of defining reaction cell ion www.atmos-meas-tech.net/11/1851/2018/ Atmos. Meas. Tech., 11, 1851–1881, 2018 1858 B. G. Heikes et al.: TS6 PCIMS instrument ion-chemistry model
Table 2. Initial reagent gas flow rates and reagent gas mixing ratios at six sample air pressures.
Sample pressure, hPaa 120 180 306 600 800 1013 b N2 flow rate, slpm 4.27 4.23 3.98 2.99 2.58 2.05 CO2 in air flow rate, slpm 0.08 0.08 0.08 0.08 0.08 0.08 CH3I in N2 flow rate, slpm 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 c CH3I, ppb 0.575 0.580 0.616 0.814 0.939 1.174 d CO2, ppm 7.36 7.42 7.88 10.42 12.02 15.02 O2, ppm 3678 3712 3941 5212 6015 7512 N2, ppm 996 322 996 288 996 059 994 788 993 866 992 488
a b ◦ Pressure in hPa (hectopascal, equivalent to milli-bars). slpm, standard liters per minute (Tref = 0 C; Pref = 1013.25 hPa). c ppb, parts per billion (molecular mixing ratio times 109). d ppm, parts per million (molecular mixing ratio times 106).
concentration and analyte ion-molecule cluster concentra- 1012 tion, included N2 (∼ 79 %), O2 (∼ 21 %), CO2 (∼ 400 ppm), CH4 (∼ 2 ppm), H2 (∼ 0.5 ppm), N2O(∼ 0.32 ppm), O3 (∼ 0.05 ppm), NO (∼ 1 ppb), NO2 (∼ 1 ppb), HNO3 (∼ 1 ppb), H2O2 (∼ 1 ppb), CH3OOH (∼ 1 ppb), HFo 1010 (∼ 1 ppb) and HAc (∼ 1 ppb). The noble gases, carbon monoxide, and other oxygenated volatile organic compounds were not considered here. The air-sample water vapor mix- 8 ing ratio was varied from 10 to 31 700 ppm to span the range -3 10 found in the troposphere. Simulation results are presented as a function of reaction cell water vapor mixing ratio and am- bient sample pressure. 106
3 Model results
4 The development of ions along the length of the ion- Ion concentration, molec cm 10 SUM source tube for representative ambient pressures of 1013 and e- 307 hPa is illustrated in Fig. 3 for the fully developed model. I- O- The total ion density was at or near steady-state approxi- 2 2 mately 2/3 s of the way through the ion source tube, although 10 O- .(CO )- − 2 2 O (CO2) increased throughout the length of the source tube O- .(O ) 2 − − 2 2 at the expense of O2 and O2 (O2) (blue traces). Distance along the length of the source tube is displayed on the x axis 100 instead of time because the time of transit through the tube 10-2 10-1 100 101 varied with air-sample pressure. Distance along 210Po source, cm − In the ion-source tube, electrons e were captured by O2 210 and dissociatively captured by CH3I: Figure 3. Ion densities – arbitrary units – along the Po source tube for flow conditions of 306 hPa ambient pressure (dashed − − M − lines) and 1013 hPa (solid lines). The predominant ion after e is e + O −→ O (1,2) − 2 2 O (CO ) and I− is the smallest. − − 2 2 e + CH3I → I + CH3 (3)
The M indicates that a third molecule participates in the re- − action. A portion of the initial O2 reacted with O2, CO2 and Note reaction numbers follow their order within the model − CH3I in the source tube and in the reaction cell yielding sec- code. Reaction (4) was inferred based on O reactivity − − − 2 ondary I and O2 (CO2) and O2 (O2) cluster ions: with CH3F, CH3Cl, CH3Br, CF4, CF3Cl, CF3Br and CF3I (Fehsenfeld et al., 1975; Streit, 1982; McDonald and Chowd- − + →→ − + + O2 CH3I I O2 CH3 (4) hury, 1985; Grimsrud, 1992; Morris, 1992; Kazil, 2002). At − + −→M − high CH3I mixing ratios such as those used in Slusher et O2 CO2 O2 (CO2) (5) al. (2004) and Le Breton (2012) without O2 or CO2, CH3I − + −→M − − O2 O2 O2 (O2) (55) initially captured the electrons and I was the primary neg-
Atmos. Meas. Tech., 11, 1851–1881, 2018 www.atmos-meas-tech.net/11/1851/2018/ B. G. Heikes et al.: TS6 PCIMS instrument ion-chemistry model 1859 ative reagent ion generated within the ion source tube. For sample O3 mixing ratio was halved, doubled or set to our reagent mixture, the model indicated approximately 20 % 500 ppb. The latter was apropos to the UTLS (upper tropo- − − of the initial electrons lead to I formation and 80 % to O2 sphere lower stratosphere). Simulated hydroperoxide and or- − − and its clusters. The secondary formation of I from O2 was ganic acid sensitivities were relatively unchanged even with small. At the end of the ion source tube, the concentrations a 10-fold increase in O3. However, as will be discussed later, − − − of the primary reagent ions: O2 ,O2 (CO2) and I , were pre- O3 influenced potential isobaric interferences at m/z 66, − 18 − dicted at comparable concentrations. O3 (H2O), and 80, O of CO3 (H2O) and the changes in O3 In the termolecular reactions above, others below, and in resulted in a nearly proportionate increase in these ions. As Appendix Table A2, M represented the concentration of all an aside to O− and CO− chemistries, O’Sullivan et al. (2018) 3 −3 other gases, mostly N2 followed by O2,H2O, Ar and CO2, proposed to use CO3 as a hydroperoxide reagent ion fol- whereas in the experiments used to determine reaction rate lowing the work of Cappa and Elrod (2001) but were un- constants, M usually represented a single predominant gas successful in its implementation. Our simulations indicated like O2, CO2, Ar or He. N2 or H2O were seldom included as O’Sullivan’s O3 reagent concentrations were likely too low. the third body. In the case of electron attachment, Pack and Figures 5a–10a show experimentally determined sensitivi- − Phelps (1966) noted faster rates of e attachment with H2O ties as a function of reaction cell water vapor mixing ratio for − − − − as the third body compared to O2 or CO2 and that rates with O2 (H2O2),O2 (CH3OOH),O2 (CO2)(H2O2),I (H2O2), − − these two gases were faster than those when N2 was the third I (HFo) and I (HAc), respectively. The field and labora- body. Under humid conditions in the reaction cell section, tory calibration data were primarily dependent upon humid- this was a potential source of error, larger than the factor of ity and secondarily on sample ambient pressure. The exper- two given above. Electron concentrations at the end of the imental data were first binned by humidity irrespective of source tube were predicted, under our assumptions, to be a ambient or sample pressure. The horizontal bar of the plus factor three larger than any of the other reagent ions. symbol denotes the limits of a reaction cell water vapor mix- Figure 4 shows the predicted concentrations of I−,O−, ing ratio bin and is plotted at the mean sensitivity for that bin. − − − 2 O2 (CO2)O3 and CO3 ions, ion-hydrates and analyte–ion The length of the vertical bar of the plus symbol indicates one clusters along the length of the reaction cell after the ion standard deviation of the bin and the variability was due to source stream was mixed with the sample air stream for the variations arising from pressure, ambient concentrations dur- fully developed model. In Fig. 4, distance along the reac- ing the standard addition, systematic variations due to water tion cell was used for the x axis for consistency with Fig. 3, vapor across a bin, calibration gas precision and instrument although the transit time through this section was constant precision. The yellow shaded portions outlined the experi- and time or distance were equivalent. The reaction cell transit mentally determined sensitivity from laboratory experiments time was 17.8 ms. Two representative simulations are shown, and field calibrations from DC3 and FRAPPE. one with an atmospheric pressure and subsequent sample Figures 5b–10b show the model simulated ion–analyte flow rate commensurate with 1013 hPa and air sample water cluster sensitivities at the end of the reaction cell as a func- vapor mixing ratio of 17 800 ppm (16 ◦C dew point tempera- tion of reaction cell water vapor mixing ratio and ambient ture) and the other with a sample pressure of 307 hPa, a com- sample pressure for the fully developed model. The simu- mensurate sample flow rate and water vapor mixing ratio of lated ion–analyte cluster sensitivities are expressed in arbi- 1000 ppm (−32 ◦C frost point temperature). The correspond- trary units as Lee et al. (2014) and Iyer et al. (2016) have ar- ing reaction cell water vapor mixing ratios were ∼ 9700 and gued instrumental factors make it nearly impossible to map ∼ 130 ppm, respectively. The ions and ion-hydrates were at simulated instrument sensitivity to that determined exper- or near steady-state approximately 1/3 of the way down imentally. However, assuming instrumental process effects the reaction cell length. The ion–analyte clusters increased were proportional for each individual ion-neutral cluster, in- steadily down the length of the cell (Fig. 4e), with the ex- strument sensitivity trends with pressure and water vapor for − − − ception of I (H2O2) and I (HAc) and possibly O2 (H2O2), each ion-neutral should be captured by the simulations and which peaked at 1 to 3 cm and then decline with distance scalable on an individual basis. “Sensitivity”, as shown, is down the remainder of the reaction cell. This was attributed the ion cluster concentration divided by the analyte’s ambient to the time needed to form the clusters of interest and their mixing ratio, 1 ppb, and was expected to be proportional to + titration after formation by ion–ion recombination with N2 . counts per ppb. These were further scaled to a maximum of 1 This suggested a longer flow tube could improve sensitivity by dividing the predicted sensitivities by the maximum sensi- for those ions which have not reached their maximum value tivity calculated for that cluster regardless of sample pressure by the end of the reaction cell but at the expense of those or humidity. clusters which have already peaked. The ambient ozone mixing ratio was set to 50 ppb in all − cases show here. No appreciable difference in O2 (H2O2), − − − − O2 (CH3OOH),O2 (CO2)(H2O2),O2 (H2O2),I (HFo) and I− (HAc) sensitivity was observed when the assumed www.atmos-meas-tech.net/11/1851/2018/ Atmos. Meas. Tech., 11, 1851–1881, 2018 1860 B. G. Heikes et al.: TS6 PCIMS instrument ion-chemistry model
Figure 4. Simulated ion cluster densities along the reaction cell path for ambient pressure of Pa = 307 hPa and reaction cell H2O = 133 ppm (dashed line) or Pa = 1013 hPa and reaction cell H2O = 9706 ppm (solid line). Ambient O3 was set equal to 50 ppb for both pressures. Reaction cell time of transit is tx = 17.8 ms. (a) Unhydrated reagent ion density. (b) First-hydrate reagent ion density. (c) Second-hydrate reagent ion densities. (d) Third-hydrate reagent ion densities. (e) Ion–analyte cluster ion density–arbitrary units.
− − − 4 Discussion I (HFo) and I (HAc), not shown. The simulated O2 hy- droperoxide cluster sensitivity showed too steep of an in- − − crease to the maximum value and then too steep of a de- The initial model mechanism including O2 ,O2 (H2O), − − − crease after the maximum as the water vapor mixing ra- O2 (CO2),I and I (H2O) alone was unable to simulate the sample pressure and water dependent trends in sensitivity for tio varied from 10 to 20 000 ppm. The maximum sensitiv- − − − − ity was at water vapor mixing ratios near a few 100 ppm. O2 (H2O2),O2 (CH3OOH),O2 (CO2)(H2O2),I (H2O2),
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−1 − · Figure 5. (a) Experimental sensitivity (counts per second per ppb, cps ppb ) trend in O2 (H2O2) as a function of reaction cell water = vapor mixing ratio (χH2O, ppm), from DC3 (red), FRAPPE (blue), and the laboratory [FCH3I 0.0005 (cyan) and 0.001 (green) slpm]. All calibrations were binned by χH2O and bin widths are shown by the horizontal lines. Vertical bars indicate one standard deviation of a bin and include sample pressure variation effects, water variation within a bin, precision of the standard addition calibration gas concentration, instrument precision and ambient mixing ratio variation across the standard addition period. There were fewer than four observations per bin in FRAPPE for water vapor mixing rations less than 103 ppm. Magenta crosses in panel (a) correspond to DC3 post mission calibrations without the addition of CH3I and after there had been multiple refills of the reagent CO2 in air bottle. (b) Normalized simulated sensitivity as a function of χH2O for six different sample pressures as shown in the legend. The yellow shading maps the trends in experimental sensitivity (a) to the calculated trends in sensitivity (b) using the same normalization process.
− Figure 6. Same as Fig. 5 except for O2 (CH3OOH).
The addition of reactions leading to higher order ion hy- 2. the inclusion of Reactions (149)–(152) allowing for drates, (H2O)n>1, carbonates, (CO2)n>1 and mixed hydrate- higher order hydrates to form the analyte cluster ions carbonates, (H2O)m(CO2)n, were included to reduce the for peroxides; steepness on each side of the maximum (see Supplement for − − 3. the inclusion of O3 reactions with O to yield O and details). − 2 3 The mechanism so modified remained insufficient to re- subsequent CO3 ions; − − produce the O2 and O2 (CO2) peroxide sensitivities as a 4. invoking a new carbonation Reaction (199), function of reaction cell H2O mixing ratio and ambient sam- ple pressure (not shown) observed in the field and labora- − + + → − O2 (H2O2) (CO2) M O2 (CO2)(H2O2) tory measurements. Multiple avenues were explored includ- + H O + M; (199) ing (see Supplement): 2 1. modification of reaction rate coefficients for Reac- 5. the addition of Reactions (204)–(209) allowing for tions (12), (13), (14), (21), (24), (147), and (148), which higher order hydrates of I− to form the analyte cluster − − − describe the O2 (H2O) (CO2) switching system; ions for hydrogen peroxide and the organic acids. www.atmos-meas-tech.net/11/1851/2018/ Atmos. Meas. Tech., 11, 1851–1881, 2018 1862 B. G. Heikes et al.: TS6 PCIMS instrument ion-chemistry model
− Figure 7. Same as Fig. 5 except for O2 (CO2)(H2O2).
− Figure 8. Same as Fig. 5 except for I (H2O2). Magenta crosses in panel (a) correspond to DC3 post mission calibrations without the addition of CH3I; there had been multiple refillings of the reagent CO2 in the air bottle and the CH3I reagent gas concentration is presumed to be very small.
The addition of O3 chemistry had little effect on sen- with rate coefficients set at approximately the collision limit sitivity, whereas the first two changes improved the pres- (3 × 10−9) were unable to simulate enough hydroperoxide sure dependent sensitivity and water vapor trends for cluster formation. − the O2 hydroperoxide clusters but did not significantly A solution to the low humidity problem was suggested improve the pressure and water vapor sensitivity trends by the work of Fehsenfeld and Ferguson (1974), Fahey et − in O2 (CO2)(H2O2), necessitating a process like Reac- al. (1982) and Böhringer et al. (1984). Böhringer et al. (1984) tion (199). suggested there is a hierarchical shift in cluster ion ligands, − Under low water vapor conditions the model under pre- X · L, according to ion–ligand bond energy (Ebond), for a − − − · dicted O2 (H2O2) and O2 (CH3OOH) at higher sample pres- specific ion. Their ordering followed: Ebond X H2O < − − sures relative to low sample pressures. This was primarily Ebond X · SO2 < Ebond X · H2O2 < − − − due to the conversion of most of the O reagent ion to Ebond X · HCl < Ebond X · HNO3 . Adams et − 2 O2 (CO2) in the absence of water vapor (e.g., Kebarle et al. (1970), Fehsenfeld and Ferguson (1974) and Fahey al., 1972). The conversion of O− to O− was of minor influ- et al. (1982) presented and discussed the thermodynamics 2 3 − − − − ence. Significantly, at higher water vapor mixing ratios, the and kinetics of O ,O (O2),O (CO2),O (H2O)n=1,3 and − − − 2 2 2 2 O2 hydroperoxide clusters and the O2 (CO2)(H2O2) clus- O2 (CO2)(H2O)n=1,3. Their bond energies suggested the ter were under predicted because of O− hydrate formation, series given by Böhringer et al. (1984) could be extended − 2 O2 (H2O)n=1,5 and the switching reactions included in the to include O2 and CO2 as ligands with O2 more weakly initial mechanism: bound than H2O and with CO2 and H2O being compara- − − − − bly bound, such that: Ebond X N2 < Ebond X O2 < O (H2O) + H2O2 → O (H2O2) + H2O (28) − − − 2 2 Ebond X H2O ≈ Ebond X CO2 < Ebond X SO2 < − + → − + O2 (H2O) CH3OOH O2 (CH3OOH) H2O (36)
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Figure 9. Same as Fig. 5 except for I−(HFo). Field calibrations for HFo were not performed in DC3.
Figure 10. Same as Fig. 9 except for I−(HAc). Field calibrations for HAc were not performed in DC3.