Real-time gas mass spectroscopy by multivariate analysis

Abstract

Early and significant results for a real-time, column-free miniaturized gas mass spectrometer in detecting target species with partial overlapping spectra are reported. The achievements have been made using both nanoscale holes as a nanofluidic sampling inlet system and a robust statistical technique. Even if the presented physical implementation could be used with gas chromatography columns, the aim of high miniaturization requires investigating its detection performance with no aid. As a study case, in the first experiment, dichloromethane (CH2Cl2) and cyclohexane (C6H12) with concentrations in the 6–93 ppm range in single and compound mixtures were used. The nano-orifice column-free approach acquired raw spectra in 60 s with correlation coefficients of 0.525 and 0.578 to the NIST reference database, respectively. Then, we built a calibration dataset on 320 raw spectra of 10 known different blends of these two compounds using partial least square regression (PLSR) for statistical data inference. The model showed a normalized full-scale root-mean-square deviation (NRMSD) accuracy of 10.9mathrm{%} and 18.4mathrm{%} for each species, respectively, even in combined mixtures. A second experiment was conducted on mixes containing two other gasses, Xylene and Limonene, acting as interferents. Further 256 spectra were acquired on 8 new mixes, from which two models were developed to predict CH2Cl2 and C6H12, obtaining NRMSD values of 6.4% and 13.9%, respectively.