Unsupervised classification of petroleum Certified Reference Materials and other fuels by chemometric analysis of gas chromatography-mass spectrometry data.

As feedstocks transition from conventional oil to unconventional petroleum sources and biomass, it will be necessary to determine whether a particular fuel or fuel blend is suitable for use in engines. Certifying a fuel as safe for use is time-consuming and expensive and must be performed for each new fuel. In principle, suitability of a fuel should be completely determined by its chemical composition. This composition can be probed through use of detailed analytical techniques such as gas chromatography-mass spectroscopy (GC-MS). In traditional analysis, chromatograms would be used to determine the details of the composition. In the approach taken in this paper, the chromatogram is assumed to be entirely representative of the composition of a fuel, and is used directly as the input to an algorithm in order to develop a model that is predictive of a fuel's suitability. When a new fuel is proposed for service, its suitability for any application could then be ascertained by using this model to compare its chromatogram with those of the fuels already known to be suitable for that application. In this paper, we lay the mathematical and informatics groundwork for a predictive model of hydrocarbon properties. The objective of this work was to develop a reliable model for unsupervised classification of the hydrocarbons as a prelude to developing a predictive model of their engine-relevant physical and chemical properties. A set of hydrocarbons including biodiesel fuels, gasoline, highway and marine diesel fuels, and crude oils was collected and GC-MS profiles obtained. These profiles were then analyzed using multi-way principal components analysis (MPCA), principal factors analysis (PARAFAC), and a self-organizing map (SOM), which is a kind of artificial neural network. It was found that, while MPCA and PARAFAC were able to recover descriptive models of the fuels, their linear nature obscured some of the finer physical details due to the widely varying composition of the fuels. The SOM was able to find a descriptive classification model which has the potential for practical recognition and perhaps prediction of fuel properties.

Fourier transform spectrometry with a near-infrared supercontinuum source.

Optical fiber based supercontinuum light sources combine the brightness of lasers with the broad bandwidth of incandescent lamps and thus are promising candidates for sources in spectroscopic applications requiring high brightness and broad bandwidth. Herein, near-infrared (IR) Fourier transform (FT) spectrometry with a supercontinuum (SC) light source is investigated. The efficient, collimated propagation of broad bandwidth SC light through an 18 m path length multipass cell is demonstrated. A normalized spectral difference is calculated for the SC spectrum on consecutive FT mirror scans and is found to vary by less than 0.5%, indicating excellent spectral stability. The rms noise on zero absorbance lines is obtained as a function of the number of mirror scans at 0.125, 2, and 16 cm(-1) resolution for both the SC and conventional tungsten lamp source. The SC source has approximately a factor of ten times more noise than the lamp under comparable conditions for each resolution and data acquisition time. This clearly indicates that spectral acquisition with the SC source is not detector noise limited. NIR-FT spectra of methane and methyl salicylate, acquired with both the SC and lamp source, are reported. These spectra illustrate the advantage the SC source has over the incandescent source in that it can efficiently traverse long path lengths, thus providing a sensitivity advantage. The spectra also demonstrate the disadvantage of the SC source with respect to the lamp in the increased level of amplitude noise. Prospects for the future use of SC sources in absorption spectroscopy, including possible noise mitigation strategies, are briefly discussed.

Quantitative vapor-phase infrared spectrometry of ammonia.

Reference spectra of ammonia from four sources are compared. Low-resolution spectra (i.e., spectra for which the spectrometer resolution is numerically greater than the full-width at half-height of the rotational lines) were obtained from the Environmental Protection Agency (EPA) web site and from Infrared Analysis, Inc. High-resolution (0.12 cm-1) spectra were obtained from the National Institute for Standards and Technology (NIST) and Pacific Northwest National Laboratory (PNNL). Two protocols were used to validate the EPA and Infrared Analysis spectra, with one requiring that Beer's law be obeyed by the low-resolution spectrum and the other that Beer's law be obeyed by the high-resolution spectrum. In all cases, the second protocol gave a significantly better spectral match. It is shown that the path-integrated concentrations for the low-resolution reference spectra were in error by as little as 4% to as much as an order of magnitude, presumably because of the effect of adsorption on the cell walls. Measured absorptivities of the NIST and PNNL spectra were different by approximately 2.6% and it is believed that the effect of adsorption on these spectra is small. When the same protocols were used to test the reference spectrum of methane, the calculated path-integrated concentration was only approximately 2% different from the one that was calculated from the NIST reference spectrum, suggesting that the data processing protocols provide accurate data.

Consistency of ozone and nitrogen oxides standards at tropospherically relevant mixing ratios.

The absolute accuracy and long-term precision of atmospheric measurements hinge on the quality of the instrumentation and calibration standards. To assess the consistency of the ozone (O3) and nitrogen oxides (NO(x)) standards maintained at the National Institute of Standards and Technology (NIST), these standards were compared through the gas-phase titration of O3 with nitric oxide (NO). NO and O3 were monitored using chemiluminescence and UV absorption, respectively. Nitrogen dioxide (NO2) was monitored directly by laser-induced fluorescence and indirectly by catalytic conversion to NO, followed by chemiluminescence. The observed equivalent loss of both NO and O3 and the formation of NO2 in these experiments was within 1% on average over the range of 40-200 nmol mol(-1) of NO in excess O3, indicating that these instruments, when calibrated with the NIST O3 and NO standards and the NO2 permeation calibration system, are consistent to within 1% at tropospherically relevant mixing ratios of O3. Experiments conducted at higher initial NO mixing ratios or in excess NO are not in as good agreement. The largest discrepancies are associated with the chemiluminescence measurements. These results indicate the presence of systematic biases under these specific conditions. Prospects for improving these experiments are discussed.

Gas-phase databases for quantitative infrared spectroscopy.

The National Institute of Standards and Technology (NIST) and the Pacific Northwest National Laboratory (PNNL) are each creating quantitative databases containing the vapor-phase infrared spectra of pure chemicals. The digital databases have been created with both laboratory and remote-sensing applications in mind. A spectral resolution of approximate, equals 0.1 cm(-1) was selected to avoid degrading sharp spectral features, while also realizing that atmospheric broadening typically limits line widths to 0.1 cm(-1). Calculated positional (wave- number, cm(-1)) uncertainty is /=9) path length-concentration burdens and fitting a weighted Beer's law plot to each wavenumber channel. The two databases include different classes of compounds and were compared using 12 samples. Though these 12 samples span a range of polarities, absorption strengths, and vapor pressures, the data agree to within experimental uncertainties with only one exception.

Removing aperture-induced artifacts from Fourier transform infrared intensity values.

Two Fourier transform infrared intensity artifacts have been observed at moderately high (0.1 cm(-1)) spectral resolution: Light reflected off the aperture was double modulated by the interferometer, producing a 2f alias, and the warm (approximately 310 K) annulus of the aperture seen by a cooled detector resulted in distorted line shapes and anomalous intensities in the fingerprint region. Although the second artifact has been alluded to previously, we report corrections to remove both of these anomalies and to demonstrate the efficacy of these corrections. Prior to correction, integrated-band intensities were found to be in error by up to 12%.