Simultaneous airborne nitric acid and formic acid measurements using a chemical ionization mass spectrometer around the UK: Analysis of primary and secondary production pathways

2014 ◽  
Vol 83 ◽  
pp. 166-175 ◽  
Author(s):  
Michael Le Breton ◽  
Asan Bacak ◽  
Jennifer B.A. Muller ◽  
Ping Xiao ◽  
Beth M.A. Shallcross ◽  
...  
Keyword(s):  
Nitric Acid ◽  
Formic Acid ◽  
Mass Spectrometer ◽  
Secondary Production ◽  
Chemical Ionization ◽  
Ionization Mass ◽  
The Uk

scholarly journals Airborne observations of formic acid using a chemical ionization mass spectrometer

2012 ◽  
Vol 5 (12) ◽  
pp. 3029-3039 ◽  
Author(s):  
M. Le Breton ◽  
M. R. McGillen ◽  
J. B. A. Muller ◽  
A. Bacak ◽  
D. E. Shallcross ◽  
...  
Keyword(s):  
Formic Acid ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Limit Of Detection ◽  
Standard Addition ◽  
Ionization Mass ◽  
Airborne Measurements ◽  
Mixing Ratios ◽  
Primary Emissions ◽  
The Uk

Abstract. The first airborne measurements of formic acid mixing ratios over the United Kingdom were measured on the FAAM BAe-146 research aircraft on 16 March 2010 with a chemical ionization mass spectrometer using I− reagent ions. The I− ionization scheme was able to measure formic acid mixing ratios at 1 Hz in the boundary layer. In-flight standard addition calibrations from a formic acid source were used to determine the instrument sensitivity of 35 ± 6 ion counts pptv−1 s−1 and a limit of detection of 25 pptv. Routine measurements were made through a scrubbed inlet to determine the instrumental background. Three plumes of formic acid were observed over the UK, originating from London, Humberside and Tyneside. The London plume had the highest formic acid mixing ratio throughout the flight, peaking at 358 pptv. No significant correlations of formic acid with NOx and ozone were found, but a positive correlation was observed between CO and HCOOH within the two plumes where coincident data were recorded. A trajectory model was employed to determine the sources of the plumes and compare modelled mixing ratios with measured values. The model underestimated formic acid concentrations by up to a factor of 2. This is explained by missing sources in the model, which were considered to be both primary emissions of formic acid of mainly anthropogenic origin and a lack of precursor emissions, such as isoprene, from biogenic sources, whose oxidation in situ would lead to formic acid formation.

scholarly journals A Chemical Ionization Mass Spectrometer for Ground-Based Measurements of Nitric Acid

2006 ◽  
Vol 23 (8) ◽  
pp. 1104-1113 ◽  
Author(s):  
Kazuyuki Kita ◽  
Yu Morino ◽  
Yutaka Kondo ◽  
Yuichi Komazaki ◽  
Nobuyuki Takegawa ◽  
...  
Keyword(s):  
Nitric Acid ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Limit Of Detection ◽  
Field Tests ◽  
Background Level ◽  
Ionization Mass ◽  
Mixing Ratios ◽  
Free Air ◽  
Diffusion Scrubber

Abstract A chemical ionization mass spectrometer (CIMS) instrument has been developed for high-precision measurements of gaseous nitric acid (HNO3) specifically under high- and variable-humidity conditions in the boundary layer. The instrument’s background signals (i.e., signals detected when HNO3-free air is measured), which depend on the humidity and HNO3 concentration of the sample air, are the most important factor affecting the limit of detection (LOD). A new system to provide HNO3-free air without changing both the humidity and the pressure of the sampled air was developed to measure the background level accurately. The detection limit was about 23 parts per trillion by volume (pptv) for 50-s averages. Field tests, including an intercomparison with the diffusion scrubber technique, were carried out at a surface site in Tokyo, Japan, in October 2003 and June 2004. A comparison between the measured concentrations of HNO3 and particulate nitrate indicated that the interference from particulate nitrate was not detectable (i.e., less than about 1%). The intercomparison indicated that the two independent measurements of HNO3 agreed to within the combined uncertainties of these measurements. This result demonstrates that the CIMS instrument developed in this study is capable of measuring HNO3 mixing ratios with the precision, accuracy, and time resolution required for atmospheric science.

scholarly journals A switchable reagent ion high resolution time-of-flight chemical ionization mass spectrometer for real-time measurement of gas phase oxidized species: characterization from the 2013 Southern Oxidant and Aerosol Study

2015 ◽  
Vol 8 (3) ◽  
pp. 3199-3244 ◽  
Author(s):  
P. Brophy ◽  
D. K. Farmer
Keyword(s):  
High Resolution ◽  
Formic Acid ◽  
Gas Phase ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Time Of Flight ◽  
Ionization Mass ◽  
Resolution Time ◽  
Limit Of Quantification ◽  
Reduced Pressure

Abstract. A novel configuration of the Aerodyne high resolution time-of-flight chemical ionization mass spectrometer (HR-TOF-CIMS) as a switchable reagent ion (SRI) HR-TOF-CIMS is presented and described along with data collected at the Southern Oxidant and Aerosol Study (SOAS) during the summer of 2013. The calibration system and reduced pressure gas-phase inlet are characterized. The average limit of detection and limit of quantification for formic acid during SOAS are 82 and 863 ppt, respectively, corresponding to an average sensitivity of 13 ± 5 Hz ppt−1. Hourly background determinations and calibrations are shown to be essential for tracking instrument performance and accurately quantifying formic acid. Maximum daytime formic acid concentrations of 10 ppb are reported during SOAS, and a strong diel cycle is observed leading to night time concentrations below the limit of quantification. Other species presented exhibit diel behavior similar to formic acid. The concept of the mass defect enhancement plot and the use of signal-to-noise are described in detail as a method for investigating HR-TOF-CIMS spectra in an effort to reduce data complexity.

scholarly journals A switchable reagent ion high resolution time-of-flight chemical ionization mass spectrometer for real-time measurement of gas phase oxidized species: characterization from the 2013 southern oxidant and aerosol study

2015 ◽  
Vol 8 (7) ◽  
pp. 2945-2959 ◽  
Author(s):  
P. Brophy ◽  
D. K. Farmer
Keyword(s):  
High Resolution ◽  
Formic Acid ◽  
Gas Phase ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Time Of Flight ◽  
Ionization Mass ◽  
Resolution Time ◽  
Limit Of Quantification ◽  
Reduced Pressure

Abstract. A novel configuration of the Aerodyne high resolution time-of-flight chemical ionization mass spectrometer (HR-TOF-CIMS) as a switchable reagent ion (SRI) HR-TOF-CIMS is presented and described along with data collected at the Southern Oxidant and Aerosol Study (SOAS) during the summer of 2013. The calibration system and reduced pressure gas phase inlet are characterized. The average limit of detection and limit of quantification for formic acid during SOAS are 82 and 863 ppt, respectively, corresponding to an average sensitivity of 13 ± 5 Hz ppt−1. Hourly background determinations and calibrations are shown to be essential for tracking instrument performance and accurately quantifying formic acid. Maximum daytime formic acid concentrations of 10 ppb are reported during SOAS, and a strong diel cycle is observed leading to nighttime concentrations below the limit of quantification. Other species presented exhibit diel behavior similar to formic acid. The concept of the mass defect enhancement plot and the use of signal-to-noise are described in detail as a method for investigating HR-TOF-CIMS spectra in an effort to reduce data complexity.

Composition of ultrafine particles in urban Beijing: Measurement using a thermal desorption chemical ionization mass spectrometer

2021 ◽  
Author(s):  
Xiaoxiao Li ◽  
Yuyang Li ◽  
Michael Lawler ◽  
Jiming Hao ◽  
James Smith ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Thermal Desorption ◽  
Ultrafine Particles ◽  
Chemical Ionization ◽  
Urban Atmosphere ◽  
Ionization Mass ◽  
Radioactive Materials ◽  
Desorption Chemical Ionization ◽  
Wide Range ◽  
Primary Emissions

<p>Ultrafine particles (UFPs) dominate the particle number population in the urban atmosphere and revealing their chemical composition is important. The thermal desorption chemical ionization mass spectrometer (TDCIMS) can semi-continuously measure UFP composition at the molecular level. We modified a TDCIMS and deployed it in urban Beijing. Radioactive materials in the TDCIMS for aerosol charging and chemical ionization were replaced by soft X-ray ionizers so that it can be operated in countries with tight regulations on radioactive materials. Protonated N-methyl-2-pyrrolidone ions were used as the positive reagent ion, which selectively detects ammonia and low-molecular weight-aliphatic amines and amides vaporized from the particle phase. With superoxide as the negative reagent ion, a wide range of inorganic and organic compounds were observed, including nitrate, sulfate, aliphatic acids with carbon numbers up to 18, and highly oxygenated CHO, CHON, and CHOS compounds. The latter two can be attributed to parent ions or the decomposition products of organonitrates and organosulfates/organosulfonates, respectively. Components from both primary emissions and secondary formation of UFPs were identified. Compared to the UFPs measured at forest and marine sites, those in urban Beijing contain more nitrogen-containing and sulfur-containing compounds. These observations illustrate unique features of the UFPs in this polluted urban environment and provide insights into their origins.</p>

scholarly journals Using collision-induced dissociation to constrain sensitivity of ammonia chemical ionization mass spectrometry (NH<sub>4</sub><sup>+</sup> CIMS) to oxygenated volatile organic compounds

2019 ◽  
Vol 12 (3) ◽  
pp. 1861-1870 ◽  
Author(s):  
Alexander Zaytsev ◽  
Martin Breitenlechner ◽  
Abigail R. Koss ◽  
Christopher Y. Lim ◽  
James C. Rowe ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Chemical Ionization Mass Spectrometry ◽  
Collision Induced Dissociation ◽  
Ionization Mass ◽  
Oxygenated Volatile Organic Compounds ◽  
Volatile Organic

Abstract. Chemical ionization mass spectrometry (CIMS) instruments routinely detect hundreds of oxidized organic compounds in the atmosphere. A major limitation of these instruments is the uncertainty in their sensitivity to many of the detected ions. We describe the development of a new high-resolution time-of-flight chemical ionization mass spectrometer that operates in one of two ionization modes: using either ammonium ion ligand-switching reactions such as for NH4+ CIMS or proton transfer reactions such as for proton-transfer-reaction mass spectrometer (PTR-MS). Switching between the modes can be done within 2 min. The NH4+ CIMS mode of the new instrument has sensitivities of up to 67 000 dcps ppbv−1 (duty-cycle-corrected ion counts per second per part per billion by volume) and detection limits between 1 and 60 pptv at 2σ for a 1 s integration time for numerous oxygenated volatile organic compounds. We present a mass spectrometric voltage scanning procedure based on collision-induced dissociation that allows us to determine the stability of ammonium-organic ions detected by the NH4+ CIMS instrument. Using this procedure, we can effectively constrain the sensitivity of the ammonia chemical ionization mass spectrometer to a wide range of detected oxidized volatile organic compounds for which no calibration standards exist. We demonstrate the application of this procedure by quantifying the composition of secondary organic aerosols in a series of laboratory experiments.

Isobutane Chemical Ionization Mass Spectrographic Examination of Explosives

1975 ◽  
Vol 58 (4) ◽  
pp. 734-742 ◽  
Author(s):  
Richard Saferstein ◽  
Jew-Ming Chao ◽  
John J Manura
Keyword(s):  
Mass Spectrometer ◽  
Mass Spectra ◽  
Thermal Instability ◽  
Chemical Ionization ◽  
High Sensitivity ◽  
Gas Pressure ◽  
Ionization Mass ◽  
Pentaerythritol Tetranitrate ◽  
Residue Detection ◽  
Acetone Extracts

Abstract The detection of explosive residues in debris is difficult because of the thermal instability of many explosives along with the high sensitivity requirements of the analyses. The isobutane chemical ionization (CI) mass spectra of common civilian and military explosives were obtained under different instrumental parameters. The intent of the study was to determine the feasibility of applying CI to residue detection. The CI spectra of the explosives 1,3,5-trinitro-1,3,5-triazocydohexane, 1,3,5,7-tetraazocyclooctane, and pentaerythritol tetranitrate were shown to be particularly sensitive to the conditions of source temperature and reagent gas pressure. These parameters were adjusted to yield the least complex CI spectra for the explosives studied. The simplicity of the CI spectra obtained makes it a feasible technique for detecting explosive residues in the presence of extraneous materials found in the acetone extracts of debris material. Placement of the extract into the direct probe of the CI mass spectrometer eliminates the need for prior chromatographic treatment of the extract and would optimize the high sensitivity of the CI technique.

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

2018 ◽  
Vol 11 (4) ◽  
pp. 1901-1920 ◽  
Author(s):  
Victoria Treadaway ◽  
Brian G. Heikes ◽  
Ashley S. McNeill ◽  
Indira K. C. Silwal ◽  
Daniel W. O'Sullivan
Keyword(s):  
Mass Spectrometry ◽  
Hydrogen Peroxide ◽  
Acetic Acid ◽  
Formic Acid ◽  
Chemical Ionization ◽  
Method Development ◽  
Ionization Mass Spectrometry ◽  
Chemical Ionization Mass Spectrometry ◽  
Ionization Mass ◽  
Ion Clusters

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.

Sign in / Sign up

Export Citation Format

Share Document