Chemical ionization tandem mass spectrometer for the in situ measurement of methyl hydrogen peroxide

A new approach for measuring gas-phase methyl hydrogen peroxide [(MHP) CH_3OOH] utilizing chemical ionization mass spectrometry is presented. Tandem mass spectrometry is used to avoid mass interferences that hindered previous attempts to measure atmospheric CH_3OOH with CF_3O− clustering chemistry. CH_3OOH has been successfully measured in situ using this technique during both airborne and ground-based campaigns. The accuracy and precision for the MHP measurement are a function of water vapor mixing ratio. Typical precision at 500 pptv MHP and 100 ppmv H_2O is ±80 pptv (2 sigma) for a 1 s integration period. The accuracy at 100 ppmv H_2O is estimated to be better than ±40%. Chemical ionization tandem mass spectrometry shows considerable promise for the determination of in situ atmospheric trace gas mixing ratios where isobaric compounds or mass interferences impede accurate measurements