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Atmospheric Reactive Trace Gas Observations in Field and Chamber Studies Using CF₃O⁻ Chemical Ionization Mass Spectrometry


Crounse, John D. (2011) Atmospheric Reactive Trace Gas Observations in Field and Chamber Studies Using CF₃O⁻ Chemical Ionization Mass Spectrometry. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/JMSN-NF98.


This dissertation describes the development of chemical ionization mass spectrometry (CIMS) instrumentation and methods utilizing the CF3O- reagent ion for the sensitive, specific, and direct detection of many oxygenated volatile organic compounds (OVOC) and inorganic reactive trace gases in the atmosphere. These species include HNO3, HONO, HO2NO2, SO2, HCN, H2O2, CH3OOH, CH3(O)OOH, HC(O)OH, CH3C(O)OH, HC(O)CH2OH, CH3C(O)CH2OH, organic hydroperoxides (ROOH), and many additional multifunctional species (e.g., hydroxynitrates, hydroxycarbonyls, hydroxyhydroperoxides, carbonylnitrates, carbonylhydroperoxides, etc.).

CF3O--tandem mass spectrometry (MSMS) is demonstrated to be useful for distinguishing and individual quantification of certain isobaric compounds, as well as solving instrumental background problems for certain species. This technology is applied in field studies conducted from aircraft and ground-based platforms and to chamber studies investigating VOC oxidation and organic aerosol formation mechanisms. Comparisons with simultaneous observations from other instrumentation for several species show good agreement with CIMS observations. CF3O--CIMS observations of HCN (a biomass burning tracer) from aircraft are used to quantify the impact of biomass burning emissions to the Mexico City region in March 2006. Biomass burning emissions are shown to contribute significantly to a number of gas and aerosol phase pollutants even in the midst of the large anthropogenic pollution emissions from Mexico City. The analysis of the photochemical aging of a fire plume over the Yucatan Peninsula (March 2006) is also reported. Observations indicate intense chemistry occurring within the fire plume evidenced by high OH levels, fast production of H2O2 and conversion of NO and NO2 (NOx) into peroxyacetylnitrate (PAN) and aerosol nitrate. This rapid chemistry is likely driven by photolysis of HONO, which is observed to be emitted in high amounts from these fires.

The CIMS methods are applied to studies of VOC oxidation and organic aerosol formation conducted in chamber experiments. Specifically, new insights gained from the study of isoprene oxidation under high and low NOx conditions are reported. We quantify the formation of small carboxylic acids as well as C5-hydroxynitrates from the oxidation of isoprene under high NOx conditions. Under low NOx conditions, we show that C5-hydroxyhydroperoxides are formed in high yield. Subsequent oxidation of these hydroxyhydroperoxides is shown to occur through a unique HOx neutral mechanism that generates C5-epoxydiols, a likely precursor to organic aerosol.

We utilize the high sensitivity and specificity of CF3O- -CIMS to study novel intermolecular hydrogen-shift isomerization processes in peroxy radicals formed during isoprene oxidation. We find these rates to be substantially slower than recent theoretical predictions; however, we find these isomerization rates to be fast enough that they are important in atmospheric isoprene oxidation in regions where lifetimes become long. Globally, we estimate 8-11% of isoprene peroxy radicals react through 1,6-H-shift isomerization reactions.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:atmospheric chemistry, trace gasses, hydrogen peroxide, hydroperoxides, CIMS, isoprene oxidation, isoprene nitrates, isoprene epoxides, isoprene SOA, peroxy radical isomerization, biomass burning emissions
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Wennberg, Paul O.
Thesis Committee:
  • Okumura, Mitchio (chair)
  • Wennberg, Paul O.
  • Seinfeld, John H.
  • Blake, Geoffrey A.
Defense Date:6 December 2010
Record Number:CaltechTHESIS:05172011-160342650
Persistent URL:
Crounse, John D.0000-0001-5443-729X
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11762
Deposited By: Kathy Johnson
Deposited On:20 Aug 2019 17:47
Last Modified:09 Oct 2019 17:05

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