Characterization and optimization of membrane inlets for a miniature ion trap mass spectrometer operating at a high background pressure of humid air

A 10-kg handheld ion trap mass spectrometer, the Mini10, operating at a high background pressure (10−4 Torr range) of humid air was characterized and optimized with respect to the use of membrane inlets. Both flat sheet and tubular membrane inlet configurations in different dimensions were tested using aqueous solutions and inlet temperatures ranging from 25 to 90 °C. The results show that both the absolute ion abundances and the relative abundance of ions in the recorded spectra of volatile organic compounds were highly influenced by the pressure in the vacuum chamber. At elevated pressures the signal intensities dropped, and a shift from primarily electron ionization to primarily chemical ionization was observed. For some chemicals unexpected high-intensity water adduct ions were observed, as confirmed by MS/MS experiments. The pressure effects were found to be correlated with the ionization potential of the analytes, the higher the ionization potential the stronger the effects. Since the pressure in the vacuum chamber is determined by both the membrane dimensions and the temperature of the inlet, the optimization of the membrane inlet is a matter of balancing membrane dimensions and inlet temperature such that both a maximal intensity and an acceptable short response time are achieved simultaneously. In contrast to what is observed for benchtop instruments, elevated inlet temperatures may lead to reduced signal intensity, and the use of a thicker membrane may increase signal intensity. Under all circumstances we found that a linear relationship between signal intensity and sample concentration was observed over at least two orders of magnitude as long as the operational conditions of the system was kept constant. The pressure effects described here are likely to be general for all miniature ion trap mass spectrometers using low performance vacuum pumps.