Direct detection of acetonitrile at the pptv level with photoinduced associative ionization time-of-flight mass spectrometry.

Photoionization mass spectrometry (PI-MS) has become a versatile tool in the real-time analysis of volatile organic compounds (VOCs) from the atmosphere or exhaled breath. However, some key species, e.g. , acetonitrile, are hard to measure due to their higher ionization energies than photon energy. In this study, the direct and sensitive detection of gaseous acetonitrile based on a photoinduced associative ionization (PAI) reaction was investigated with a laboratory-built PAI time-of-flight mass spectrometer (PAI-TOFMS). By doping CH 2 Cl 2 in the photoionization ion source, the mass signal of acetonitrile that cannot be effectively obtained by photoionization appeared with an extremely high intensity through the PAI reaction between acetonitrile, CH 2 Cl 2 , and residual H 2 O in the system. Though the moisture in the sample gas has an evident impact on the detection efficiency of acetonitrile, with a relative signal intensity decreasing from 100% under dry conditions to 60% at saturated relative humidity, excellent detection sensitivity was still obtained for gaseous acetonitrile in different matrixes. The sensitivity calibration experiment showed that the detection sensitivities of acetonitrile in N 2 buffer gas, exhaled gas, and outdoor air were 682.4 ± 5.2, 17.0 ± 0.7, and 23.9 ± 0.2 counts pptv -1 , respectively, with an analysis time of 10 s. The corresponding 3 σ LODs reached 0.22, 8.82, and 6.28 pptv, which are equivalent to 0.40, 16.0, and 11.4 ng m -3 . The performance of the PAI-TOFMS was first demonstrated by analyzing exhaled acetonitrile from healthy non-smokers and smokers and continuous monitoring of acetonitrile in outdoor air. In summary, this study provides a new and highly sensitive method for the real-time detection of acetonitrile through mass spectrometry.