scholarly journals Application of chemical derivatization techniques combined with chemical ionization mass spectrometry to detect stabilized Criegee intermediates and peroxy radicals in the gas phase

2021 ◽  
Vol 14 (3) ◽  
pp. 2501-2513
Author(s):  
Alexander Zaytsev ◽  
Martin Breitenlechner ◽  
Anna Novelli ◽  
Hendrik Fuchs ◽  
Daniel A. Knopf ◽  
...  
Keyword(s):  
Gas Phase ◽  
Chemical Ionization ◽  
Laboratory Experiments ◽  
Spin Trapping ◽  
Integration Time ◽  
Ionization Mass ◽  
Peroxy Radicals ◽  
Chemical Derivatization ◽  
Spin Traps ◽  
Criegee Intermediates

Abstract. Short-lived highly reactive atmospheric species, such as organic peroxy radicals (RO2) and stabilized Criegee intermediates (SCIs), play an important role in controlling the oxidative removal and transformation of many natural and anthropogenic trace gases in the atmosphere. Direct speciated measurements of these components are extremely helpful for understanding their atmospheric fate and impact. We describe the development of an online method for measurements of SCIs and RO2 in laboratory experiments using chemical derivatization and spin trapping techniques combined with H3O+ and NH4+ chemical ionization mass spectrometry (CIMS). Using chemical derivatization agents with low proton affinity, such as electron-poor carbonyls, we scavenge all SCIs produced from a wide range of alkenes without depleting CIMS reagent ions. Comparison between our measurements and results from numeric modeling, using a modified version of the Master Chemical Mechanism, shows that the method can be used for the quantification of SCIs in laboratory experiments with a detection limit of 1.4×107 molecule cm−3 for an integration time of 30 s with the instrumentation used in this study. We show that spin traps are highly reactive towards atmospheric radicals and form stable adducts with them by studying the gas-phase kinetics of the reaction of spin traps with the hydroxyl radical (OH). We also demonstrate that spin trap adducts with SCIs and RO2 can be simultaneously probed and quantified under laboratory conditions with a detection limit of 1.6×108 molecule cm−3 for an integration time of 30 s for RO2 species with the instrumentation used in this study. Spin trapping prevents radical secondary reactions and cycling, ensuring that measurements are not biased by chemical interferences, and it can be implemented for detecting RO2 species in laboratory studies and potentially in the ambient atmosphere.

scholarly journals Application of chemical derivatization techniques combined with chemical ionization mass spectrometry to detect stabilized Criegee intermediates and peroxy radicals in the gas phase

2020 ◽  
Author(s):  
Alexander Zaytsev ◽  
Martin Breitenlechner ◽  
Anna Novelli ◽  
Hendrik Fuchs ◽  
Daniel A. Knopf ◽  
...  
Keyword(s):  
Gas Phase ◽  
Chemical Ionization ◽  
Laboratory Experiments ◽  
Spin Trapping ◽  
Chemical Ionization Mass Spectrometry ◽  
Integration Time ◽  
Ionization Mass ◽  
Peroxy Radicals ◽  
Chemical Derivatization ◽  
Criegee Intermediates

Abstract. Short-lived highly reactive atmospheric species, such as organic peroxy radicals (RO2) and stabilized Criegee intermediates (SCIs), play an important role in controlling the oxidative removal and transformation of many natural and anthropogenic trace gases in the atmosphere. Direct speciated measurements of these components are extremely helpful for understanding their atmospheric fate and impact. We describe the development of an online method for measurements of SCIs and RO2 in laboratory experiments using chemical derivatization and spin trapping techniques combined with H3O+ and NH4+ chemical ionization mass spectrometry (CIMS). Using chemical derivatization agents with low proton affinity, such as electron-poor carbonyls, we scavenge all SCIs produced from a wide range of alkenes without depleting CIMS reagent ions. Comparison between our measurements and results from numeric modelling, using a modified version of the Master Chemical Mechanism, shows that the method can be used for quantification of SCIs in laboratory experiments with detection limit of 1.4 × 107 molecule cm-3 for 30 s integration time with the instrumentation used in this study. We show that spin traps are highly reactive towards atmospheric radicals and form stable adducts with them by studying the gas-phase kinetics of their reaction with hydroxyl radical (OH). We also demonstrate that spin trap adducts with SCIs and RO2 can be simultaneously probed and quantified under laboratory conditions with detection limit of 1.6 × 108 molecule cm-3 for 30  s integration time for RO2 species with the instrumentation used in this study. Spin trapping prevents radical secondary reactions and cycling, which ensures that measurements are not biased by chemical interferences, and can be implemented for detecting RO2 species in the ambient atmosphere.

scholarly journals Detection of dimethylamine in the low pptv range using nitrate chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry

2016 ◽  
Vol 9 (5) ◽  
pp. 2135-2145 ◽  
Author(s):  
Mario Simon ◽  
Martin Heinritzi ◽  
Stephan Herzog ◽  
Markus Leiminger ◽  
Federico Bianchi ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Atmospheric Pressure ◽  
Chemical Ionization ◽  
Integration Time ◽  
Ionization Mass ◽  
Mixing Ratios ◽  
Highly Sensitive ◽  
Volatile Organic ◽  
Cluster Ion

Abstract. Amines are potentially important for atmospheric new particle formation, but their concentrations are usually low with typical mixing ratios in the pptv range or even smaller. Therefore, the demand for highly sensitive gas-phase amine measurements has emerged in the last several years. Nitrate chemical ionization mass spectrometry (CIMS) is routinely used for the measurement of gas-phase sulfuric acid in the sub-pptv range. Furthermore, extremely low volatile organic compounds (ELVOCs) can be detected with a nitrate CIMS. In this study we demonstrate that a nitrate CIMS can also be used for the sensitive measurement of dimethylamine (DMA, (CH3)2NH) using the NO3−•(HNO3)1 − 2• (DMA) cluster ion signal. Calibration measurements were made at the CLOUD chamber during two different measurement campaigns. Good linearity between 0 and  ∼  120 pptv of DMA as well as a sub-pptv detection limit of 0.7 pptv for a 10 min integration time are demonstrated at 278 K and 38 % RH.

scholarly journals Technical note: Detection of dimethylamine in the low pptv range using nitrate Chemical Ionization-Atmospheric Pressure interface-Time Of Flight (CI-APi-TOF) mass spectrometry

2015 ◽  
Vol 8 (12) ◽  
pp. 13257-13284
Author(s):  
M. Simon ◽  
M. Heinritzi ◽  
S. Herzog ◽  
M. Leiminger ◽  
F. Bianchi ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Chemical Ionization ◽  
Technical Note ◽  
Integration Time ◽  
Ionization Mass ◽  
Highly Sensitive ◽  
Volatile Organic ◽  
Aerosol Chamber ◽  
Cluster Ion

Abstract. Amines are potentially important for atmospheric new particle formation and therefore the demand for highly sensitive gas phase amine measurements has emerged in the last several years. Nitrate Chemical Ionization Mass Spectrometry (CIMS) is routinely used for the measurement of gas phase-sulfuric acid in the sub-pptv range. Furthermore, Extremely Low Volatile Organic Compounds (ELVOCs) can be detected with a nitrate CIMS. In this study we demonstrate that a nitrate CIMS can also be used for the sensitive measurement of dimethylamine ((CH3)2NH, DMA) using the NO3−(HNO3)1-2(DMA) cluster ion signals. This observation was made at the CLOUD aerosol chamber, which was also used for calibration measurements. Good linearity between 0 and ~120 pptv of DMA as well as a sub-pptv detection limit of 0.7 pptv for a 10 min integration time are demonstrated at 278 K and 38 % RH.

scholarly journals Chemical ionization mass spectrometry (CIMS) may not measure all gas-phase sulfuric acid if base molecules are present

2010 ◽  
Vol 10 (12) ◽  
pp. 30539-30568
Author(s):  
T. Kurtén ◽  
T. Petäjä ◽  
J. Smith ◽  
I. K. Ortega ◽  
M. Sipilä ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Sulfuric Acid ◽  
Gas Phase ◽  
Chemical Ionization ◽  
Measurement Data ◽  
Ionization Mass Spectrometry ◽  
Chemical Ionization Mass Spectrometry ◽  
Ionization Mass ◽  
Proton Affinities ◽  
Reaction Thermodynamics

Abstract. The state-of-the art method for measuring atmospheric gas-phase sulfuric acid is chemical ionization mass spectrometry (CIMS) based on nitrate reagent ions. Using computed proton affinities and reaction thermodynamics for the relevant charging reactions, we show that in the presence of strong bases such as amines, which tend to cluster with the sulfuric acid molecules, a significant fraction of the total gas-phase sulfuric acid may not be measured by a CIMS instrument. If this is the case, this effect has to be taken into account in the interpretation of atmospheric sulfuric acid measurement data, as well as in intercomparison of different CIMS instruments, which likely have different susceptibilities to amine-sulfuric acid clustering.

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