Application of PARAFAC for calibration with excitation-emission matrix fluorescence spectra of three classes of environmental pollutants

Abstract

Parallel factor analysis (PARAFAC) is applied to three calibrations of a field-portable, cuvette-based, singlemeasurement, excitation-emission matrix fluorometer. In the first example the fluorometer is calibrated based on interactions between a non-fluorescent DDT-type pesticide and a fluorescent dye. PARAFAC is employed to deconvolve the fluorescence profiles of dissociated and complexed dye states. Calibration is performed based on the intensity of dye-pesticide fluorescence. In the second example, weighted PARAFAC (W-PARAFAC) is applied to determination of three polynuclear aromatic hydrocarbons (PAHs). The weighted algorithm is required to incorporate saturated channels of the CCD detector into the calibration model. In the third example, W-PARAFAC is applied to calibration of two carbamate pesticides. The weighted algorithm is required to account for Rayleigh and Raman scattering overlapping with the fluorescence spectra. For theses three applications, parts-per-trillion to parts-per-billion detection limits are observed in aqueous solutions. Copyright

Practical aspects of PARAFAC modeling of fluorescence excitation‐emission data

“…It was shown that tryptophan and tyrosine and also high molecular weight Maillard reaction polymers and polyphenolic compounds were important fluorophores. In an investigation of the interactions between a nonfluorescent DDT-type pesticide and a fluorescent dye, PARAFAC was employed to find the fluorescence profiles of complexed dye states [9]. Furthermore, the ability to quantify trace pesticides and polycyclic aromatic hydrocarbons by fluorescence spectroscopy and PARAFAC modeling was investigated by Jiji et al [10].…”

A regularized nonnegative canonical polyadic decomposition algorithm with preprocessing for 3D fluorescence spectroscopy

“…In fact, the fluorescent DOM fractions that are generally observed in surface water, and that provide water quality information, are protein-like -indicator of microbial activity and humiclike -indicator of terrestrial activity. Many studies have shown that fluorescence spectroscopy can characterize natural organic matter [2] and detect different types of aquatic pollutants, like sewage, petroleum products or pesticides [59][60][61][62][63][64]. But another possible application could be the understanding of the interaction between metals salts (like uranyl ion or its complexes) and DOM (or soil fulvic acids) [65] to be able to develop a method or a device to monitor and predict the transport of radioactive metals in aquatic systems.…”

Robust Calibration

“…The observed value x ijk then corresponds to the intensity of sample i at emission wavelength j and excitation wavelength k. [112][113][114] The scores and loadings of the PARAFAC model are estimated by minimizing the objective function The PARAFAC model is often used to decompose fluorescence data into trilinear components according to the number of fluorophores (F) present in the samples.…”