scholarly journals An aircraft-borne chemical ionization – ion trap mass spectrometer (CI-ITMS) for fast PAN and PPN measurements

2010 ◽  
Vol 3 (5) ◽  
pp. 4313-4354
Author(s):  
A. Roiger ◽  
H. Aufmhoff ◽  
P. Stock ◽  
F. Arnold ◽  
H. Schlager
Keyword(s):  
Boundary Layer ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Ion Trap ◽  
The Arctic ◽  
Arctic Boundary Layer ◽  
Online Calibration ◽  
Mixing Ratios ◽  
Ion Trap Mass Spectrometer ◽  
Research Aircraft

Abstract. An airborne chemical ionization ion trap mass spectrometer instrument (CI-ITMS) has been developed for tropospheric and stratospheric fast in-situ measurements of PAN (peroxyacetyl nitrate) and PPN (peroxypropionyl nitrate). The first scientific deployment of the FASTPEX instrument (FASTPEX = Fast Measurement of Peroxyacyl nitrates) took place in the Arctic during 18 missions aboard the DLR research aircraft Falcon, within the framework of the POLARCAT-GRACE campaign in the summer of 2008. The FASTPEX instrument is described and characteristic properties of the employed ion trap mass spectrometer are discussed. Atmospheric data obtained at altitudes of up to ~12 km are presented, from the boundary layer to the lowermost stratosphere. Data were sampled with a time resolution of 2 s and a 2σ detection limit of 25 pmol mol−1. An isotopically labelled standard was used for a permanent online calibration. For this reason the accuracy of the PAN measurements is better than ±10% for mixing ratios greater than 200 pmol mol−1. PAN mixing ratios in the summer Arctic troposphere were in the order of a few hundred pmol mol−1 and generally correlated well with CO. In the Arctic boundary layer and lowermost stratosphere smaller PAN mixing ratios were observed due to a combination of missing local sources of PAN precursor gases and efficient removal processes (thermolysis/photolysis). PPN, the second most abundant PAN homologue, was measured simultanously. Observed PPN/PAN ratios range between ~0.03 and 0.3.

scholarly journals An aircraft-borne chemical ionization – ion trap mass spectrometer (CI-ITMS) for fast PAN and PPN measurements

2011 ◽  
Vol 4 (2) ◽  
pp. 173-188 ◽  
Author(s):  
A. Roiger ◽  
H. Aufmhoff ◽  
P. Stock ◽  
F. Arnold ◽  
H. Schlager
Keyword(s):  
Boundary Layer ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Ion Trap ◽  
The Arctic ◽  
Arctic Boundary Layer ◽  
Mixing Ratios ◽  
Ion Trap Mass Spectrometer ◽  
Research Aircraft ◽  
On Line

Abstract. An airborne chemical ionization ion trap mass spectrometer instrument (CI-ITMS) has been developed for tropospheric and stratospheric fast in-situ measurements of PAN (peroxyacetyl nitrate) and PPN (peroxypropionyl nitrate). The first scientific deployment of the FASTPEX instrument (FASTPEX = Fast Measurement of Peroxyacyl nitrates) took place in the Arctic during 18 missions aboard the DLR research aircraft Falcon, within the framework of the POLARCAT-GRACE campaign in the summer of 2008. The FASTPEX instrument is described and characteristic properties of the employed ion trap mass spectrometer are discussed. Atmospheric data obtained at altitudes of up to ~12 km are presented, from the boundary layer to the lowermost stratosphere. Data were sampled with a time resolution of 2 s and a 2σ detection limit of 25 pmol mol−1. An isotopically labelled standard was used for a permanent on-line calibration. For this reason the accuracy of the PAN measurements is better than ±10% for mixing ratios greater than 200 pmol mol−1. PAN mixing ratios in the summer Arctic troposphere were in the order of a few hundred pmol mol−1 and generally correlated well with CO. In the Arctic boundary layer and lowermost stratosphere smaller PAN mixing ratios were observed due to a combination of missing local sources of PAN precursor gases and efficient removal processes (thermolysis/photolysis). PPN, the second most abundant PAN homologue, was measured simultaneously. Observed PPN/PAN ratios range between ~0.03 and 0.3.

scholarly journals Signature of Arctic surface ozone depletion events in the isotope anomaly (Δ<sup>17</sup>O) of atmospheric nitrate

2007 ◽  
Vol 7 (5) ◽  
pp. 1451-1469 ◽  
Author(s):  
S. Morin ◽  
J. Savarino ◽  
S. Bekki ◽  
S. Gong ◽  
J. W. Bottenheim
Keyword(s):  
Boundary Layer ◽  
Ozone Depletion ◽  
Surface Ozone ◽  
The Arctic ◽  
Arctic Boundary Layer ◽  
Mixing Ratios ◽  
Atmospheric Nitrate ◽  
Boundary Layer Ozone ◽  
Oxidation Of No ◽  
Arctic Surface

Abstract. We report the first measurements of the oxygen isotope anomaly of atmospheric inorganic nitrate from the Arctic. Nitrate samples and complementary data were collected at Alert, Nunavut, Canada (82°30 ' N, 62°19 ' W) in spring 2004. Covering the polar sunrise period, characterized by the occurrence of severe boundary layer ozone depletion events (ODEs), our data show a significant correlation between the variations of atmospheric ozone (O3) mixing ratios and Δ17O of nitrate (Δ17O(NO−3)). This relationship can be expressed as: Δ17O(NO−3)/‰, =(0.15±0.03)×O3/(nmol mol–1)+(29.7±0.7), with R2=0.70(n=12), for Δ17O(NO−3) ranging between 29 and 35 ‰. We derive mass-balance equations from chemical reactions operating in the Arctic boundary layer, that describe the evolution of Δ17O(NO−3) as a function of the concentrations of reactive species and their isotopic characteristics. Changes in the relative importance of O3, RO2 and BrO in the oxidation of NO during ODEs, and the large isotope anomalies of O3 and BrO, are the driving force for the variability in the measured Δ17O(NO−3) . BrONO2 hydrolysis is found to be a dominant source of nitrate in the Arctic boundary layer, in agreement with recent modeling studies.

Self chemical ionization in an ion trap mass spectrometer

1988 ◽  
Vol 60 (20) ◽  
pp. 2312-2314 ◽  
Author(s):  
Scott A. McLuckey ◽  
Gary L. Glish ◽  
Keiji G. Asano ◽  
Gary J. Van Berkel
Keyword(s):  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Ion Trap ◽  
Ion Trap Mass Spectrometer

Chemical ionization in an ion trap mass spectrometer

1987 ◽  
Vol 59 (9) ◽  
pp. 1278-1285 ◽  
Author(s):  
Jennifer S. Brodbelt ◽  
John N. Louris ◽  
R. Graham. Cooks
Keyword(s):  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Ion Trap ◽  
Ion Trap Mass Spectrometer

Letter: Hydroxide and Oxygen Atom Attachment to Dichlorophthalic Anhydride in Negative-Ion Chemical Ionization with Collisionally-Activated Dissociation in an External-Source Ion Trap Mass Spectrometer

2002 ◽  
Vol 8 (4) ◽  
pp. 329-332 ◽  
Author(s):  
Hui-Fen Wu ◽  
Chien-Hung Chen
Keyword(s):  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Ion Trap ◽  
External Source ◽  
Negative Ion ◽  
Molecule Reaction ◽  
Ion Trap Mass Spectrometer ◽  
Collisionally Activated Dissociation ◽  
Fragment Ions ◽  
Negative Ion Chemical Ionization

This study reports the investigation of some unusual adduct ions of hydroxide and oxygen atoms in both negative-ion chemical ionization (NCI) and collisionally-activated dissociation (CAD) processes in an external-source ion trap mass spectrometer. The [M + OH]− and [M + OH – Cl]− adduct ions in the NCI spectrum of 4,5-dichlorophthalic anhydride are attributed to an ion/molecule reaction due to the presence of trace amounts of water. The formation of the unusual [M + O – Cl]− ions during CAD of the M− ions from 3,6-and 4,5-dichlorophthalic anhydride isomers is attributed to reactive collisions of the fragment ions with residual oxygen.

Study of Ion—Molecule Reactions and Collisionally-Activated Dissociation of Dopamine and Adrenaline by an Ion Trap Mass Spectrometer with An External Ionization Source

2000 ◽  
Vol 6 (1) ◽  
pp. 65-77 ◽  
Author(s):  
Hui-Fen Wu ◽  
Ya-Ping Lin
Keyword(s):  
Mass Spectrometer ◽  
Reaction Mechanisms ◽  
Chemical Ionization ◽  
Ion Trap ◽  
Hydroxyl Group ◽  
Amino Group ◽  
Reactive Site ◽  
Ionization Source ◽  
Ion Trap Mass Spectrometer ◽  
Ion Molecule Reactions

Study of the reaction mechanisms for ion–molecule reactions and for collisionally-activated dissociations (CAD) of dopamine and adrenaline has been performed using an external chemical ionization source quadrupole ion trap mass spectrometer. This work demonstrates the possibility of applying an external source ion trap instrument to perform selective ion–molecule reactions in the gas phase, due to its high sensitivity and low detection limits in mass spectrometry/mass spectrometry (MS/MS) mode. CAD experiments on ions with relative intensity as low as 0–2%, formed as ion–molecule products of dopamine and adrenaline, have been successfully performed. Study of some fragment ions of M+• and [M + H]+, observed in the chemical ionization (CI) spectra, by CAD techniques, permits elucidation of a series of mechanisms for the sequential dissociations of the M+• and [M + H]+ ions. Thus, the structural information obtained from this method is similar to that which would have been obtained if MS n had been performed for M+• and [M + H]+ ions. From the proposed CAD reaction mechanisms and the semi-empirical calculations, the favored reactive sites for formation of the adduct ions could be determined. The reactive site for protonation of dopamine is on the amino group, but for adrenaline, it is on the benzylic hydroxyl group. As to the reactive site for the CH3O=C2H+ ion addition, dopamine is either on the amino group or on the phenyl ring. However, adrenaline is only on the benzylic hydroxyl group. Temperature effects on the formation of the ion–molecule products were also investigated. It was shown that the best source temperature for formation of [M + H]+ and [M + 13]+ ions of dopamine is 200°C. Information about use of dimethyl ether (DME) as the reagent gas in the external chemical ionization of an ion trap mass spectrometer is provided.

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