[Joo2010a] "Quantification of interferences in PTR-MS measurements of monoterpene emissions from Fagus sylvatica L. using simultaneous TD-GC-MS measurements",
International Journal of Mass Spectrometry
, vol. 291, no. 1: Elsevier, pp. 90–95, 2010.
The interest in quantitative analysis of biogenic volatile organic compounds (BVOCs) emissions stems from their importance in atmospheric chemistry. In order to compare the most frequently used BVOC measurement techniques, simultaneous on-line PTR-MS and off-line GC-MS data collection was performed on a 3 years old Fagus sylvatica L. tree placed in a growth chamber. Using an internal standard (deuterated toluene) and applying the selective ion mode (SIM) resulted in significant improvements of monoterpene (MT) quantification by TD-GC-MS. PTR-MS quantification of MTs was based on the ion signal at m/z 137. In the course of the experiments the relative contribution of linalool compared to that of MTs was found to be up to 84%. Since this compound has also a PTR-MS signature at m/z 137, quantification of MT emission rates by PTR-MS was disturbed. Comparison of GC-MS and PTR-MS data allowed an estimation of the ratio of the PTR-MS sensitivity for linalool to the one for MTs at m/z 137. This ratio of sensitivities, combined with the information of the relative contribution of linalool to the sum of linalool and MTs obtained by GC-MS, resulted in accurate derivation of the sum of emission rates of linalool and MTs by PTR-MS. The results indicate that fast and on-line PTR-MS measurements of BVOCs are best accompanied by off-line GC measurements to detect possible interferences or to use the additional information for properly quantifying the sum of emission rates of several compounds.
[Mielke2010] "Quantitative determination of biogenic volatile organic compounds in the atmosphere using proton-transfer reaction linear ion trap mass spectrometry.",
, vol. 82, no. 19: Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA., pp. 7952–7957, Oct, 2010.
Although oxidation of biogenic volatile organic compounds (BVOCs) plays an important role in tropospheric ozone and secondary organic aerosol production, significant uncertainties remain in our understanding of the impacts of BVOCs on ozone, aerosols, and climate. To quantify BVOCs, the proton-transfer reaction linear ion trap (PTR-LIT) mass spectrometer was previously developed. The PTR-LIT represents an improvement over more traditional techniques (including the proton-transfer reaction mass spectrometer), providing the capability to directly quantify and differentiate isomeric compounds by MS/MS analysis, with better time resolution and minimal sample handling, compared to gas chromatography techniques. Herein, we present results from the first field deployment of the PTR-LIT. During the Program for Research on Oxidants: Photochemistry, Emissions and Transport (PROPHET) summer 2008 study in northern Michigan, the PTR-LIT successfully quantified isoprene, total monoterpenes, and isomeric isoprene oxidation products methyl vinyl ketone and methacrolein at sub-parts per billion (nmol/mol) levels in a complex forest atmosphere. The utility of the fast time response of the PTR-LIT was shown by the measurement of rapid changes in isoprene, methyl vinyl ketone, and methacrolein, concurrent with changing ozone mole fractions. Overall, the PTR-LIT was shown to be a viable field instrument with the necessary sensitivity, selectivity, and time response to provide detailed measurements of BVOC mole fractions in complex atmospheric samples, at trace levels.