Newly developed instrumentation for measuring highly oxidized molecules at atmospheric pressure

Author(s):  
Paap Koemets ◽  
Sander Mirme ◽  
Kuno Kooser ◽  
Heikki Junninen

<p>The Highly Oxidized Molecule Ion Spectrometer (HOMIS) is a novel instrument for measuring the total concentration of highly oxidized molecules (HOM-s) (Bianchi et al., 2019) at atmospheric pressure. The device combines a chemical ionization charger with a multi-channel differential mobility analyzer. The chemical ionization charger is based on the principles outlined by Eisele and Tanner (1993). The charger is attached to a parallel differential mobility analyzer identical to the ones used in the Neutral cluster and Air Ion Spectrometer (NAIS, Mirme 2011), but with modified sample and sheath air flow rates to improve the mobility resolution of the device. The complete mobility distribution in the range from 3.2 to 0.056 cm<sup>2</sup>/V/s is measured simultaneously by 25 electrometers. The range captures the charger ions, monomers, dimers, trimers but also extends far towards larger particles to possibly detect larger HOM-s that have not been measured with existing instrumentation. The maximum time resolution of the device is 1 second allowing it to detect rapid changes in the sample. The device has been designed to be easy to use, require little maintenance and work reliably in various environments during long term measurements.</p><p>First results of the prototype were acquired from laboratory experiments and ambient measurements. Experiments were conducted at the Laboratory of Environmental Physics, University of Tartu. The sample was drawn from a reaction chamber where alpha-pinene and ozone were introduced. Initial results show a good response when concentrations of alpha-pinene and ozone were changed. </p><p>Ambient measurements were conducted at the SMEAR Estonia measurement station in a hemiboreal forest for 10 days in the spring and two months in the winter of 2020. The HOMIS measurements were performed together with a CI-APi-TOF (Jokinen et al., 2012).</p><p> </p><p>References:</p><p>Bianchi, F., Kurtén, T., Riva, M., Mohr, C., Rissanen, M. P., Roldin, P., Berndt, T., Crounse, J. D., Wennberg, P. O., Mentel, T. F., Wildt, J., Junninen, H., Jokinen, T., Kulmala, M., Worsnop, D. R., Thornton, J. A., Donahue, N., Kjaergaard, H. G. and Ehn, M. (2019), “Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol”, Chemical Reviews, 119, 6, 3472–3509</p><p>Eisele, F. L., Tanner D. J. (1993), “Measurement of the gas phase concentration of H2SO4 and methane sulfonic acid and estimates of H2SO4 production and loss in the atmosphere”, JGR: Atmospheres, 98, 9001-9010</p><p>Jokinen T., Sipilä M., Junninen H., Ehn M., Lönn G., Hakala J., Petäjä T., Mauldin III R. L., Kulmala M., and Worsnop D. R. (2012), “Atmospheric sulphuric acid and neutral cluster measurements using CI-APi-TOF”, Atmospheric Chemistry and Physics, 12, 4117–4125</p><p>Mirme, S. (2011), “Development of nanometer aerosol measurement technology”, Doctoral thesis, University of Tartu</p>

2012 ◽  
Vol 12 (9) ◽  
pp. 4117-4125 ◽  
Author(s):  
T. Jokinen ◽  
M. Sipilä ◽  
H. Junninen ◽  
M. Ehn ◽  
G. Lönn ◽  
...  

Abstract. The first ambient measurements using nitrate ion based Chemical Ionization with the Atmospheric Pressure interface Time-Of-Flight mass spectrometer (CI-APi-TOF) for sulphuric acid and neutral cluster detection are presented. We have found CI-APi-TOF a highly stable and sensitive tool for molecular sulphuric acid detection. The lowest limit of detection for sulphuric acid was determined to be 3.6 × 104 molecules cm−3 for 15 min averaging. Signals from sulphuric acid clusters up to tetramer containing ammonia were also obtained but these were found to result from naturally charged clusters formed by ion induced clustering in the atmosphere during nucleation. Opposite to earlier studies with cluster mass spectrometers, we had no indication of neutral clusters. The reason is either less efficient charging of clusters in comparison to molecular sulphuric acid, or the low concentration of neutral clusters at our measurement site during these particular nucleation events. We show that utilizing high resolution mass spectrometry is crucial in separating the weak sulfuric acid cluster signal from other compounds.


2011 ◽  
Vol 11 (12) ◽  
pp. 31983-32002 ◽  
Author(s):  
T. Jokinen ◽  
M. Sipilä ◽  
H. Junninen ◽  
M. Ehn ◽  
G. Lönn ◽  
...  

Abstract. The first ambient measurements using nitrate ion based Chemical Ionization with the Atmospheric Pressure interface Time-Of-Flight mass spectrometer (CI-APi-TOF) for sulphuric acid and neutral cluster detection are presented. We have found CI-APi-TOF a highly stable and sensitive tool for molecular sulphuric acid detection. The lowest limit of detection for sulphuric acid was determined to be 3 × 104 molecules cm−3 for two hour averaging. Signals from sulphuric acid clusters up to tetramer accompanied by ammonia were also obtained but these were found to result from naturally charged clusters formed by ion induced clustering in the atmosphere during nucleation. Opposite to earlier studies with cluster mass spectrometers, we had no indication of neutral clusters. The reason is either less efficient charging of clusters in comparison to molecular sulphuric acid, or in low concentration of neutral clusters at our measurement site during these particular nucleation events. We show that utilizing high resolution mass spectrometry is crucial in separating the weak sulfuric acid cluster signal from the other compounds.


1995 ◽  
Vol 73 (12) ◽  
pp. 2263-2271 ◽  
Author(s):  
Christine C.Y. Chow ◽  
John M. Goodings

A pair of laminar, premixed, CH4–O2 flames above 2000 K at atmospheric pressure, one fuel-rich (FR) and the other fuel-lean (FL), were doped with ~10−6 mol fraction of the second-row transition metals Y, Zr, Nb, and Mo. Since these hydrocarbon flames contain natural ionization, metallic ions were produced in the flames by the chemical ionization (CI) of metallic neutral species, primarily by H3O+ and OH− as CI sources. Both positive and negative ions of the metals were observed as profiles of ion concentration versus distance along the flame axis by sampling the flames through a nozzle into a mass spectrometer. For yttrium, the observed ions include the YO+•nH2O (n = 0–3) series, and Y(OH)4−. With zirconium, they include the ZrO(OH)+•nH2O (n = 0–2) series, and ZrO(OH)3−. Those observed with niobium were the cations Nb(OH)3+ and Nb(OH)4+, and the single anion NbO2(OH)2−. For molybdenum, they include the cations MoO(OH)2+ and MoO(OH)3+, and the anions MoO3− and MoO3(OH)−. Not every ion was observed in each flame; the FL flame tended to favour the ions in higher oxidation states. Also, flame ions in higher oxidation states were emphasized for these second-row transition metals compared with their first-row counterparts. Some ions written as members of hydrate series may have structures different from those of simple hydrates; e.g., YO+•H2O = Y(OH)2+ and ZrO(OH)+•H2O = Zr(OH)3+, etc. The ion chemistry for the production of these ions by CI in flames is discussed in detail. Keywords: transition metals, ions, flame, gas phase, negative ions.


2008 ◽  
Vol 80 (8) ◽  
pp. 2646-2653 ◽  
Author(s):  
Francisco J. Andrade ◽  
Jacob T. Shelley ◽  
William C. Wetzel ◽  
Michael R. Webb ◽  
Gerardo Gamez ◽  
...  

2018 ◽  
Author(s):  
Andrea C. Wagner ◽  
Anton Bergen ◽  
Sophia Brilke ◽  
Claudia Fuchs ◽  
Markus Ernst ◽  
...  

Abstract. A new method for size resolved chemical analysis of nucleation mode aerosol particles (size range from ~ 10 to ~ 30 nm) is presented. The Thermal Desorption Differential Mobility Analyzer (TD-DMA) uses an online, discontinuous principle. The particles are charged, a specific size is selected by differential mobility analysis and they are collected on a filament by electrostatic precipitation. Subsequently, the sampled mass is evaporated in a clean carrier gas and analyzed by a chemical ionization mass spectrometer. Gas phase measurements are performed with the same mass spectrometer during the sampling of particles. The characterization shows reproducible results, with a particle size resolution of 1.19 and the transmission efficiency for 15 nm particles being slightly above 50 %. The signal from the evaporation of a test substance can be detected starting from 0.01 ng and shows a linear response in the mass spectrometer. Instrument operation in the range of pg/m3 is demonstrated by an example measurement of 15 nm particles produced by nucleation from dimethylamine, sulfuric acid and water.


2019 ◽  
Vol 21 (20) ◽  
pp. 10470-10476 ◽  
Author(s):  
Chenxi Li ◽  
Christopher J. Hogan Jr

Atmospheric pressure differential mobility analysis-mass spectrometry facilitates determination of nano-ion-neutral reaction rates approaching the collision controlled limit.


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