On stratospheric acetonitrile detection by passive chemical ionization mass spectrometry

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Acetonitrile, Atmospheric Composition, Mass Spectroscopy, Stratosphere, Abundance, Accuracy, Balloon-Borne Instruments, Molecular Ions

Scientific paper

Systematic ECA (Electric Field-induced Collisional Activation) studies of H(+)(CH3CN)m(H2O)n cluster ions were carried out in the laboratory and in balloon-borne ion mass spectrometer experiments in the stratosphere. It was found that these ions, as a result of ECA, may become converted to H(+)(H2O)n clusters. As a consequence, acetonitrile (CH3CN) abundances inferred from stratospheric ambient ion composition measurements by consideration of the measured abundance ratio for H(+)(CH3CN)m(H2O)n and H(+)(H2O)n ions are too low by factors up to about 10 depending on altitude and experimental conditions. By contrast, data obtained above about 35 km are only little affected. Building on recent aircraft-borne acetonitrile measurements, one-dimensional model calculations of the acetonitrile abundance are carried out which reproduce quite well those data not being severely affected by ECA if low atmospheric hydroxyl radical abundances are considered.

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