Calibration Transfer Algorithm for Automated Qualitative Analysis by Passive Fourier Transform Infrared Spectrometry

• Published in: Analytical chemistry (Washington) Vol. 72; no. 7; pp. 1690 - 1698
• Main Authors: Koehler, Small, Gary W, Combs, Roger J, Knapp, Robert B, Kroutil, Robert T
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01.04.2000
• Subjects: Algorithms; Analysis methods; Analytical chemistry; Applied sciences; Atmospheric pollution; Calibration; Chemistry; Exact sciences and technology; Pollution; Scientific imaging; Spectrometric and optical methods; Discriminant analysis; Data analysis; Chemical analysis; Molecular structure; Interelement effect; Air; Pattern recognition; Multivariate analysis; Remote sensing; Environmental control; Infrared spectrometry; Backpropagation algorithm; Multicomponent analysis; Feedforward neural nets; Sulfur hexafluoride; Air pollution; Qualitative analysis; Chemometrics; Acetone; Piecewise linearization
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/ac9907888

The automated qualitative analysis of passive Fourier transform infrared (FT-IR) remote sensing data is made difficult by the presence in the data of background and instrument-specific variation. For data collected with a single instrument, variation in the data arises from changes in the infrared background radiance, changes in the atmospheric composition within the field-of-view of the spectrometer, and changes in the instrument response function arising from temperature variation in the spectrometer. When more than one spectrometer is used, the variation in detector responses and phase signatures between instruments serves to complicate further the task of implementing an automated processing algorithm for detecting the signature of a target compound. In this work, a combination of signal processing and pattern recognition methodology is applied directly to the interferogram data collected by the FT-IR spectrometer to implement an automated compound detection procedure that is independent of background and instrument-specific variation. The key to this algorithm is the use of highly attenuating digital filters to isolate in the interferogram the frequencies associated with an analyte absorption or emission band while suppressing information at other frequencies. For the test compounds, acetone and sulfur hexafluoride, it is demonstrated that when this digital filtering procedure is coupled with either piecewise linear discriminant analysis or a back-propagation neural network, an automated detection algorithm can be developed with data from a primary instrument and then subsequently used to predict the presence of analyte signatures in data collected with a secondary spectrometer. Correct classification rates in excess of 92% are obtained for both compounds when the algorithm is applied to data collected with the secondary instrument.