scholarly journals Formation of 3-methyl-1,2,3-butanetricarboxylic acid via gas phase oxidation of pinonic acid – a mass spectrometric study of SOA aging

2012 ◽  
Vol 12 (3) ◽  
pp. 1483-1496 ◽  
Author(s):  
L. Müller ◽  
M.-C. Reinnig ◽  
K. H. Naumann ◽  
H. Saathoff ◽  
T. F. Mentel ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Atmospheric Pressure Chemical Ionization ◽  
Analytical Techniques ◽  
Mass Spectrometric Study ◽  
Mass Spectrometric ◽  
Oxidation Products ◽  
Acid Oxidation ◽  
Ionization Mass ◽  
Institute Of Technology

Abstract. This paper presents the results of mass spectrometric investigations of the OH-initiated oxidative aging of α-pinene SOA under simulated tropospheric conditions at the large aerosol chamber facility AIDA, Karlsruhe Institute of Technology. In particular, the OH-initiated oxidation of pure pinic and pinonic acid, two well-known oxidation products of α-pinene, was investigated. Two complementary analytical techniques were used, on-line atmospheric pressure chemical ionization/mass spectrometry (APCI/MS) and filter sampling followed by liquid chromatography/mass spectrometry (LC/ESI-MS). The results show that 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a very low volatile α-pinene SOA product and a tracer compound for terpene SOA, is formed from the oxidation of pinonic acid and that this oxidation takes place in the gas phase. This finding is confirmed by temperature-dependent aging experiments on whole SOA formed from α-pinene, in which the yield of MBTCA scales with the pinonic acid fraction in the gas phase. Based on the results, several feasible gas-phase radical mechanisms are discussed to explain the formation of MBTCA from OH-initiated pinonic acid oxidation.

scholarly journals Formation of 3-methyl-1,2,3-butanetricarboxylic acid via gas phase oxidation of pinonic acid – a mass spectrometric study of SOA aging

2011 ◽  
Vol 11 (7) ◽  
pp. 19443-19476 ◽  
Author(s):  
L. Müller ◽  
M. C. Reinnig ◽  
K. H. Naumann ◽  
H. Saathoff ◽  
T. F. Mentel ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Atmospheric Pressure Chemical Ionization ◽  
Analytical Techniques ◽  
Mass Spectrometric Study ◽  
Mass Spectrometric ◽  
Oxidation Products ◽  
Acid Oxidation ◽  
Ionization Mass ◽  
Institute Of Technology

Abstract. This paper presents the results of mass spectrometric investigations of the OH-initiated oxidative aging of α-pinene SOA under simulated tropospheric conditions at the large aerosol chamber facility AIDA, Karlsruhe Institute of Technology. In particular, the OH-initiated oxidation of pure pinic and pinonic acid, two well-known oxidation products of α-pinene, was investigated. Two complementary analytical techniques were used, on-line atmospheric pressure chemical ionization/mass spectrometry (APCI/MS) and filter sampling followed by liquid chromatography/mass spectrometry (LC/ESI-MS). The results show that 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known and very low volatile α-pinene SOA product, is formed from the oxidation of pinonic acid and that this oxidation takes place in the gas phase. This finding is confirmed by temperature-dependent aging experiments on whole SOA formed from α-pinene, in which the yield of MBTCA scales with the pinonic acid fraction in the gas phase. Based on the results, several feasible gas-phase radical mechanisms are discussed to explain the formation of MBTCA from OH-initiated pinonic acid oxidation.

scholarly journals Formation of Highly Oxygenated Low-Volatility Products from Cresol Oxidation

2016 ◽  
Author(s):  
Rebecca H. Schwantes ◽  
Katherine A. Schilling ◽  
Renee C. McVay ◽  
Hanna Lignell ◽  
Matthew M. Coggon ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Ring Opening ◽  
Chemical Ionization ◽  
First Generation ◽  
Direct Analysis ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Ionization Mass ◽  
Particle Phase

Abstract. Hydroxyl radical (OH) oxidation of toluene produces the ring-retaining products cresol and benzaldehyde, and the ring-opening products bicyclic intermediate compounds and epoxides. Here, first- and later-generation OH oxidation products from cresol and benzaldehyde are identified in laboratory chamber experiments. For benzaldehyde, first-generation ring-retaining products are identified, but later-generation products are not detected. For cresol, low-volatility (saturation mass concentration, C* ~ 3.5 × 104–7.7 × 10−3 μg m−3) first- and later-generation ring-retaining products are identified. Subsequent OH addition to the aromatic ring of o-cresol leads to compounds such as hydroxy, dihydroxy, and trihydroxy methyl benzoquinones and dihydroxy, trihydroxy, tetrahydroxy, and pentahydroxy toluenes. These products are detected in the gas phase by chemical ionization mass spectrometry (CIMS) and in the particle phase using offline direct analysis in real time mass spectrometry (DART-MS). Our data suggest that the yield of trihydroxy toluene from dihydroxy toluene is substantial. While an exact yield cannot be reported as authentic standards are unavailable, we find that a yield for trihydroxy toluene from dihydroxy toluene of ~ 0.7 (equal to the yield of dihydroxy toluene from o-cresol) is consistent with experimental results for o-cresol oxidation under low-NO conditions. These results suggest that even though the cresol pathway accounts for only ~ 20 % of the oxidation products of toluene, it is the source of a significant fraction (~ 20–40 %) of toluene secondary organic aerosol (SOA) due to the formation of low-volatility products.

Electrospray ionization mass spectrometric study of thallium complexes with nucleosides

2017 ◽  
Vol 23 (5) ◽  
pp. 300-304
Author(s):  
Magdalena Frańska
Keyword(s):  
Mass Spectrometry ◽  
Electrospray Ionization ◽  
Electrospray Ionization Mass Spectrometry ◽  
Mass Spectrometric Study ◽  
Mass Spectrometric ◽  
Ionization Mass Spectrometry ◽  
Ionization Mass ◽  
Spectrometric Study ◽  
Relative Affinity ◽  
Relative Abundances

The complexes between Tl+, K+, and nucleosides were studied by using electrospray ionization mass spectrometry. It was found that for complexes of 1:1 stoichiometry, thallium complexes with cytidine were the most abundant and thallium complexes with guanosine were the second most abundant ones. The relative abundances of cytidine–Tl+ to cytidine–K+ complexes depended on stoichiometry (at higher stoichiometry the potassium complexes were more abundant). In other words, the relative affinity of Tl+ and K+ to form cytidine complexes depends on the stoichiometry of the formed complexes. Guanosine–Tl+ complexes were more abundant than guanosine–K+ complexes, irrespective of stoichiometry. Both guanosine tetramer and mixed cytidine/guanosine tetramer were more abundant when they were stabilized by thallium than potassium. Therefore, Tl+ may affect the K+ stabilization of these tetramers.

scholarly journals Chemistry of α-pinene and naphthalene oxidation products generated in a Potential Aerosol Mass (PAM) chamber as measured by acetate chemical ionization mass spectrometry

2014 ◽  
Vol 7 (7) ◽  
pp. 6385-6429 ◽  
Author(s):  
P. S. Chhabra ◽  
A. T. Lambe ◽  
M. R. Canagaratna ◽  
H. Stark ◽  
J. T. Jayne ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Organic Acids ◽  
Gas Phase ◽  
Chemical Ionization ◽  
Oxidation Products ◽  
Ionization Mass Spectrometry ◽  
Chemical Ionization Mass Spectrometry ◽  
Ionization Mass ◽  
Aerosol Formation ◽  
Ion Chemistry

Abstract. Recent developments in high resolution, time-of-flight chemical ionization mass spectrometry (HR-ToF-CIMS) have made possible the direct detection of atmospheric organic compounds in real-time with high sensitivity and with little or no fragmentation, including low volatility, highly oxygenated organic vapors that are precursors to secondary organic aerosol formation. Here, for the first time, we examine gas-phase O3 and OH oxidation products of α-pinene and naphthalene formed in the PAM flow reactor with an HR-ToF-CIMS using acetate reagent ion chemistry. Integrated OH exposures ranged from 1.2 × 1011 to 9.7 × 1011 molec cm−3 s, corresponding to approximately 1.0 to 7.5 days of equivalent atmospheric oxidation. Measured gas-phase organic acids are similar to those previously observed in environmental chamber studies. For both precursors, we find that acetate-CIMS spectra capture both functionalization (oxygen addition) and fragmentation (carbon loss) as a function of OH exposure. The level of fragmentation is observed to increase with increased oxidation. We present a method that estimates vapor pressures of organic molecules using the measured O/C ratio, H/C ratio, and carbon number for each compound detected by the CIMS. The predicted condensed-phase SOA average acid yields and O/C and H/C ratios agree within uncertainties with previous AMS measurements and ambient CIMS results. While acetate reagent ion chemistry is used to selectively measure organic acids, in principle this method can be applied to additional reagent ion chemistries depending on the application.

Electrospray Ionization Mass Spectrometric Study of the Gas-Phase Coordination Chemistry of Be2+ Ions with 1,2- and 1,3-Diketone Ligands

2019 ◽  
Vol 58 (9) ◽  
pp. 6388-6398 ◽  
Author(s):  
Onyekachi Raymond ◽  
Penelope J. Brothers ◽  
Magnus R. Buchner ◽  
Joseph R. Lane ◽  
Matthias Müller ◽  
...  
Keyword(s):  
Coordination Chemistry ◽  
Electrospray Ionization ◽  
Gas Phase ◽  
Mass Spectrometric Study ◽  
Mass Spectrometric ◽  
Ionization Mass ◽  
Spectrometric Study ◽  
Phase Coordination

scholarly journals Formation of highly oxygenated low-volatility products from cresol oxidation

2017 ◽  
Vol 17 (5) ◽  
pp. 3453-3474 ◽  
Author(s):  
Rebecca H. Schwantes ◽  
Katherine A. Schilling ◽  
Renee C. McVay ◽  
Hanna Lignell ◽  
Matthew M. Coggon ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Ring Opening ◽  
Chemical Ionization ◽  
First Generation ◽  
Direct Analysis ◽  
Organic Aerosol ◽  
Oxidation Products ◽  
Ionization Mass ◽  
Particle Phase

Abstract. Hydroxyl radical (OH) oxidation of toluene produces ring-retaining products: cresol and benzaldehyde, and ring-opening products: bicyclic intermediate compounds and epoxides. Here, first- and later-generation OH oxidation products from cresol and benzaldehyde are identified in laboratory chamber experiments. For benzaldehyde, first-generation ring-retaining products are identified, but later-generation products are not detected. For cresol, low-volatility (saturation mass concentration, C* ∼ 3.5  ×  104 − 7.7  ×  10−3 µg m−3), first- and later-generation ring-retaining products are identified. Subsequent OH addition to the aromatic ring of o-cresol leads to compounds such as hydroxy, dihydroxy, and trihydroxy methyl benzoquinones and dihydroxy, trihydroxy, tetrahydroxy, and pentahydroxy toluenes. These products are detected in the gas phase by chemical ionization mass spectrometry (CIMS) and in the particle phase using offline direct analysis in real-time mass spectrometry (DART-MS). Our data suggest that the yield of trihydroxy toluene from dihydroxy toluene is substantial. While an exact yield cannot be reported as authentic standards are unavailable, we find that a yield for trihydroxy toluene from dihydroxy toluene of ∼ 0.7 (equal to the reported yield of dihydroxy toluene from o-cresol; Olariu et al., 2002) is consistent with experimental results for o-cresol oxidation under low-NO conditions. These results suggest that even though the cresol pathway accounts for only ∼ 20 % of the oxidation products of toluene, it is the source of a significant fraction (∼ 20–40 %) of toluene secondary organic aerosol (SOA) due to the formation of low-volatility products.

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