scholarly journals Quantification of hydroxyacetone and glycolaldehyde using chemical ionization mass spectrometry

2011 ◽  
Vol 11 (8) ◽  
pp. 23619-23653 ◽  
Author(s):  
K. M. Spencer ◽  
M. R. Beaver ◽  
J. M. St. Clair ◽  
J. D. Crounse ◽  
F. Paulot ◽  
...  

Abstract. Chemical ionization mass spectrometry (CIMS) enables online, fast, in situ detection and quantification of hydroxyacetone and glycolaldehyde. Two different CIMS approaches are demonstrated employing the strengths of single quadrupole mass spectrometry and triple quadrupole (tandem) mass spectrometry. Both methods are capable of the measurement of hydroxyacetone, an analyte with minimal isobaric interferences. Tandem mass spectrometry provides direct separation of the isobaric compounds glycolaldehyde and acetic acid using distinct, collision-induced dissociation daughter ions. Measurement of hydroxyacetone and glycolaldehyde by these methods was demonstrated during the ARCTAS-CARB 2008 campaign and the BEARPEX 2009 campaign. Enhancement ratios of these compounds in ambient biomass burning plumes are reported for the ARCTAS-CARB campaign. BEARPEX observations are compared to simple photochemical box model predictions of biogenic volatile organic compound oxidation at the site.

2014 ◽  
Vol 14 (8) ◽  
pp. 4251-4262 ◽  
Author(s):  
J. M. St. Clair ◽  
K. M. Spencer ◽  
M. R. Beaver ◽  
J. D. Crounse ◽  
F. Paulot ◽  
...  

Chemical ionization mass spectrometry (CIMS) enables online, rapid, in situ detection and quantification of hydroxyacetone and glycolaldehyde. Two different CIMS approaches are demonstrated employing the strengths of single quadrupole mass spectrometry and triple quadrupole (tandem) mass spectrometry. Both methods are generally capable of the measurement of hydroxyacetone, an analyte with known but minimal isobaric interferences. Tandem mass spectrometry provides direct separation of the isobaric compounds glycolaldehyde and acetic acid using distinct, collision-induced dissociation daughter ions. The single quadrupole CIMS measurement of glycolaldehyde was demonstrated during the ARCTAS-CARB (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites - California Air Resources Board) 2008 campaign, while triple quadrupole CIMS measurements of glycolaldehyde and hydroxyacetone were demonstrated during the BEARPEX (Biosphere Effects on Aerosols and Photochemistry Experiment) 2009 campaign. Enhancement ratios of glycolaldehyde in ambient biomass-burning plumes are reported for the ARCTAS-CARB campaign. BEARPEX observations are compared to simple photochemical box model predictions of biogenic volatile organic compound oxidation at the site.


2009 ◽  
Vol 2 (1) ◽  
pp. 119-151 ◽  
Author(s):  
J. P. Kercher ◽  
T. P. Riedel ◽  
J. A. Thornton

Abstract. We report a new method for the simultaneous in situ detection of nitryl chloride (ClNO2) and dinitrogen pentoxide (N2O5) using chemical ionization mass spectrometry (CIMS). The technique relies on the formation and detection of iodide ion-molecule clusters, I(ClNO2)− and I(N2O5)−. The novel N2O5 detection scheme is direct. It does not suffer from high and variable chemical interferences, which are associated with the typical method of nitrate anion detection. We address the role of water vapor, electric field strength, and instrument zero determinations, which influence the overall sensitivity and detection limit of this method. For both species, the method demonstrates high sensitivity (>1 Hz/pptv), precision (~10% for 100 pptv in 1 s), and accuracy (~20%), the latter ultimately determined by the nitrogen dioxide (NO2) cylinder calibration standard and characterization of inlet effects. For the typically low background signals (<10 Hz) and high selectivity, we estimate signal-to-noise (S/N) ratios of 2 for 1 pptv in 60 s averages, but uncertainty associated with the instrumental zero currently leads to an ultimate detection limit of ~5 pptv for both species. We validate our approach for the simultaneous in situ measurement of ClNO2 and N2O5 while on board the Research Vessel (RV) Knorr as part of the ICEALOT 2008 Field Campaign.


2009 ◽  
Vol 2 (1) ◽  
pp. 193-204 ◽  
Author(s):  
J. P. Kercher ◽  
T. P. Riedel ◽  
J. A. Thornton

Abstract. We report a new method for the simultaneous in situ detection of nitryl chloride (ClNO2) and dinitrogen pentoxide (N2O5) using chemical ionization mass spectrometry (CIMS). The technique relies on the formation and detection of iodide ion-molecule clusters, I(ClNO2)− and I(N2O5)−. The novel N2O5 detection scheme is direct. It does not suffer from high and variable chemical interferences, which are associated with the typical method of nitrate anion detection. We address the role of water vapor, CDC electric field strength, and instrument zero determinations, which influence the overall sensitivity and detection limit of this method. For both species, the method demonstrates high sensitivity (>1 Hz/pptv), precision (~10% for 100 pptv in 1 s), and accuracy (~20%), the latter ultimately determined by the nitrogen dioxide (NO2) cylinder calibration standard and characterization of inlet effects. For the typically low background signals (<10 Hz) and high selectivity, we estimate signal-to-noise (S/N) ratios of 2 for 1 pptv in 60 s averages, but uncertainty associated with the instrumental zero currently leads to an ultimate detection limit of ~5 pptv for both species. We validate our approach for the simultaneous in situ measurement of ClNO2 and N2O5 while on board the R/V Knorr as part of the ICEALOT 2008 Field Campaign.


1994 ◽  
Vol 72 (2) ◽  
pp. 345-351 ◽  
Author(s):  
R.J. Helleur ◽  
Pierre Thibault

The operating conditions for pyrolysis–desorption ammonia chemical ionization mass spectrometry and tandem mass spectrometry have been optimized and the technique evaluated for the production and analysis of structurally-informative pyrolytic fragmentation ions corresponding to intact anhydrohexose oligosaccharides, using amylose as the model polysaccharide. Among the various parameters examined it was found that the nature of the solvent used to adhere the sample to the emitter coil and the configuration of the emitter and the rate at which it is heated all play important roles in determining the efficiency of the pyrolytic process and the production of high mass fragment ions. Adjustment of reagent gas pressure together with source temperature also influence the chemical integrity of high mass oligomeric pyrolysis products. Under optimal operating conditions using ammonia reagent gas, the analyses of cellulose, laminarin, agars, and chitin gave relatively abundant ions corresponding to ammonium (or protonated) adducts of up to anhydrohexose tetrasaccharide. More importantly, the generation of such higher mass fragment ions provided a sustained ionic current of sufficient duration to perform tandem mass spectrometric analyses.


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