Multi-way partial least-squares and residual bi-linearization for the direct determination of monohydroxy-polycyclic aromatic hydrocarbons on octadecyl membranes via room-temperature fluorescence excitation emission matrices

    Authors

    H. C. Goicoechea; K. Calimag-Williams;A. D. Campiglia

    Comments

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    Abbreviated Journal Title

    Anal. Chim. Acta

    Keywords

    Second-order multivariate calibration; Solid-phase extraction; Room-temperature fluorescence; Excitation-emission matrices; Urine; analysis; SOLID-PHASE EXTRACTION; 2ND-ORDER MULTIVARIATE CALIBRATION; WATER; SAMPLES; LIQUID-CHROMATOGRAPHY; POLYCHLORINATED-BIPHENYLS; MASS-SPECTROMETRY; CURVE RESOLUTION; URINE; METABOLITES; QUANTIFICATION; Chemistry, Analytical

    Abstract

    Multi-way partial least-squares (N-PLS) is combined to the residual bi-linearization procedure (RBL) for the direct analysis of metabolites of polycyclic aromatic hydrocarbons in urine samples. Metabolite analysis is carried out via a two-step experimental procedure based on solid-phase extraction and room temperature fluorescence spectroscopy. Excitation-emission matrices are recorded from octadecyl (C18) membranes that serve as solid substrates for sample extraction and spectroscopic measurements. Excellent metabolite recoveries were obtained in all cases, which varied from 96.2 +/- 1.35% (9-hydroxyphenanthrene) to 99.7 +/- 0.49% (3-hydroxybenzo[a]pyrene). Background correction of extraction membranes is carried out with a new alternating least-squares (ALS) procedure adapted to second order data. The performance of N-PLS/RBL is compared to the well-established multivariate curve resolution-alternating least-squares (MCR-ALS) algorithm. Both algorithms provided similar analytical figures of merit, including their ability to handle unknown interference in urine samples. With only 10 mL of sample, the limits of detection varied between 0.06-0.08 ng mL(-1) (1-hydroxypyrene) and 0.016-0.018 ng mL(-1) (2-hydroxyfluorene). When compared to previously reported univariate calibration data, the limits of detection via N-PLS/RBL and MCR-ALS are approximately one order of magnitude higher. This was somehow expected due to the effect of unexpected components in multivariate figures of merit, i.e. a more realistic approach to the analysis of metabolites in human urine samples. (C) 2011 Elsevier B.V. All rights reserved.

    Journal Title

    Analytica Chimica Acta

    Volume

    717

    Publication Date

    1-1-2012

    Document Type

    Article

    Language

    English

    First Page

    100

    Last Page

    109

    WOS Identifier

    WOS:000301566200012

    ISSN

    0003-2670

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