Interpolation of the scattering areas in fluorescence excitation-emission matrices is a useful preprocessing method in fluorescence spectroscopy and data modelling. Commonly used row-by-row interpolation using piecewise cubic Hermite interpolating polynomials smoother (PCHIP), however, frequently leads to artifacts because it does not make any use of the information in the other dimension. We have suggested the way of constructing the penalty matrices for Whittaker smoothing that removed one of the main sources of difference between the axis of multiparametric signal - the grid step size - thus making it possible to reduce the number of parameters to optimize. We have compared Whittaker smoother with various surface interpolation methods, including LOESS, Kriging, multilevel B-spline approximation, and PCHIP for the purpose of data preprocessing before PARAFAC modelling of fluorescence signal on a model dataset. The two leaders by signal reconstruction and reconstruction of PARAFAC loadings are LOESS and Whittaker smoothing; the latter is additionally shown to have fundamentally interpretable parameters, which are easier to optimise for the whole dataset. Moreover, Whittaker keeps the shape of the signal and is resistant to variations in data structure and noise level that is very important in numerous applications. We also tested smoothers performance for Åsmund Rinnan fluorescence dataset and the high performance of Whittaker was proved. We can recommend the Whittaker smoothing as a perfect tool for interpolation of scattering areas in florescence spectra of seawaters with low signal-to-noise ratio.
Keywords: Fluorescence; PARAFAC; Rayleigh and Raman scattering; Surface interpolation; Whittaker smoothing.
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