Abstract

A calibration transfer method, piecewise direct standardization (PDS), was applied to a set of two-component samples measured on the same UV-visible spectrometer with the use of a cuvette cell with a 10-mm pathlength and a fiber-optic probe with a 2-mm pathlength. Piecewise direct standardization proceeds by determining a structured transformation matrix using the spectra of a few samples measured with both devices. This transformation matrix can then be used to transform any spectrum measured on one device to that obtained on another device, thereby making the calibration model transferable between devices. We used the spectra measured in a cuvette as the standard set and transferred the calibration model obtained for these spectra to spectra measured with a 2-mm fiberoptic probe on the same instrument. The total standard error of prediction (SEP) for the fiber-optic probe was 5.84 before the calibration transfer and 1.87 afterwards. Spectra were also processed by taking the Fourier transform prior to the calibration transfer. The 512 data points in each spectrum were compressed to 32 terms, starting with the first term after the dc offset. This processing reduced the background and the noise. As a consequence, in the Fourier domain, the total SEP was 5.69 before the calibration standardization and 0.79 after the calibration standardization. A calibration transfer was also performed between two fiber-optic probes; the total SEP in the spectral domain was 2.16 prior to the transfer and 1.04 after the transfer, whereas in the Fourier domain the SEP was 1.50 prior to the transfer and 0.77 after the transfer.

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