Real-time gas mass spectroscopy by multivariate analysis
Leonardo Franceschelli, Carla Ciricugno, Maurizio Di Lorenzo, Aldo Romani, Annachiara Berardinelli, Marco Tartagni, Raffaele Correale
Abstract
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 (CH 2 Cl 2 ) and cyclohexane (C 6 H 12 ) 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 $$10.9\mathrm{\%}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mn>10.9</mml:mn> <mml:mo>%</mml:mo> </mml:mrow> </mml:math> and $$18.4\mathrm{\%}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mn>18.4</mml:mn> <mml:mo>%</mml:mo> </mml:mrow> </mml:math> 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 CH 2 Cl 2 and C 6 H 12 , obtaining NRMSD values of 6.4% and 13.9%, respectively.