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We present four unique prediction techniques, combined with multiple data pre-processing methods, utilizing a wide range of both oil types and oil peroxide values (PV) as well as incorporating natural aging for peroxide creation. Samples were PV assayed using a standard starch titration method, AOCS Method Cd 8-53, and used as a verified reference method for PV determination. Near-infrared (NIR) spectra were collected from each sample in two unique optical pathlengths (OPLs), 2 and 24 mm, then fused into a third distinct set. All three sets were used in partial least squares (PLS) regression, ridge regression, LASSO regression, and elastic net regression model calculation. While no individual regression model was established as the best, global models for each regression type and pre-processing method show good agreement between all regression types when performed in their optimal scenarios. Furthermore, small spectral window size boxcar averaging shows prediction accuracy improvements for edible oil PVs. Best-performing models for each regression type are: PLS regression, 25 point boxcar window fused OPL spectral information RMSEP = 2.50; ridge regression, 5 point boxcar window, 24 mm OPL, RMSEP = 2.20; LASSO raw spectral information, 24 mm OPL, RMSEP = 1.80; and elastic net, 10 point boxcar window, 24 mm OPL, RMSEP = 1.91. The results show promising advancements in the development of a full global model for PV determination of edible oils. 

A new hyperspectral Raman imaging technique is described using a spatial heterodyne Raman spectrometer (SHRS) and a microlens array (MLA). The new technique enables the simultaneous acquisition of Raman spectra over a wide spectral range at spatially isolated locations within two spatial dimensions ( x, y) using a single exposure on a charge-coupled device (CCD) or other detector types such as a complementary metal-oxide semiconductor (CMOS) detector. In the SHRS system described here, a 4 × 4 mm MLA with 1600, 100 µm diameter lenslets is used to image the sample, with each lenslet illuminating a different region of the SHRS diffraction gratings and forming independent fringe images on the CCD. The fringe images from each lenslet contain the fully encoded Raman spectrum of the region of the sample “seen” by the lenslet. Since the SHRS requires no moving parts, all fringe images can be measured simultaneously with a single detector exposure, and in principle using a single laser shot, in the case of a pulsed laser. In this proof of concept paper, hyperspectral Raman spectra of a wide variety of heterogeneous samples are used to characterize the technique in terms of spatial and spectral resolution tradeoffs. It is shown that the spatial resolution is a function of the diameter of the MLA lenslets, while the number of spatial elements that can be resolved is equal to the number of MLA lenslets that can be imaged onto the SHRS detector. The spectral resolution depends on the spatial resolution desired, and the number of grooves illuminated on both diffraction gratings by each lenslet, or combination of lenslets in cases where they are grouped. 

A spatial heterodyne Raman spectrometer (SHRS), constructed using a modular optical cage and lens tube system, is described for use with a commercial silica and a custom single-crystal (SC) sapphire fiber Raman probe. The utility of these fiber-coupled SHRS chemical sensors is demonstrated using 532 nm laser excitation for acquiring Raman measurements of solid (sulfur) and liquid (cyclohexane) Raman standards as well as real-world, plastic-bonded explosives (PBX) comprising 1,3,5- triamino- 2,4,6- trinitrobenzene (TATB) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) energetic materials. The SHRS is a fixed grating-based dispersive interferometer equipped with an array detector. Each Raman spectrum was extracted from its corresponding fringe image (i.e., interferogram) using a Fourier transform method. Raman measurements were acquired with the SHRS Littrow wavelength set at the laser excitation wavelength over a spectral range of ∼1750 cm −1 with a spectral resolution of ∼8 cm −1 for sapphire and ∼10 cm −1 for silica fiber probes. The large aperture of the SHRS allows much larger fiber diameters to be used without degrading spectral resolution as demonstrated with the larger sapphire collection fiber diameter (330 μm) compared to the silica fiber (100 μm). Unlike the dual silica fiber Raman probe, the dual sapphire fiber Raman probe did not include filtering at the fiber probe tip nearest the sample. Even so, SC sapphire fiber probe measurements produced less background than silica fibers allowing Raman measurements as close as ∼85 cm −1 to the excitation laser. Despite the short lengths of sapphire fiber used to construct the sapphire probe, well-defined, sharp sapphire Raman bands at 420, 580, and 750 cm −1 were observed in the SHRS spectra of cyclohexane and the highly fluorescent HMX-based PBX. SHRS measurements of the latter produced low background interference in the extracted Raman spectrum because the broad band fluorescence (i.e., a direct current, or DC, component) does not contribute to the interferogram intensity (i.e., the alternating current, or AC, component). SHRS spectral resolution, throughput, and signal-to-noise ratio are also discussed along with the merits of using sapphire Raman bands as internal performance references and as internal wavelength calibration standards in Raman measurements.