Liquid chromatography with multivariate detection and chemometric data processing: a basis for gree-analytical methods

R. PELLEGRINO, M. CARABAJAL, G. IBAÑEZ, J. ARANCIBIA, G. ESCANDAR

Barcelona

Congreso; XVI Chemometric in Analytical Chemistry; 2016

The general objective of the present work wasthe development of methods based on green-analytical chemistry principles for the quantification of organicpollutants in complex samples, by coupling liquid chromatography,multivariate detection and chemometrics data processing.            Liquid chromatography with dualUV/diode array (DAD) and fluorescence (FLD) detections was carried out in asingle run, and the second-order DAD-elution time and FLD-elution time dataobtained were treated with MCR-ALS (multivariate curve resolution/alternatingleast-squares) algorithm. In this way, while analytes are measured through theirmore appropriate (absorbance and/or fluorescence) signals, chemometrictreatment of the corresponding matrices allows the resolution of total or partial overlapped bands,and to overcome the presence of interferences in real samples.            Thetwo investigated systems involved emerging contaminants belonging to plasticsderived endocrine disruptors (bisphenol A, nonylphenol, octylphenol, diethylphtalate, dibutyl phthalate and diethylhexyl phthalate), and ten agrochemicalsof frequent use, namely fungicides, herbicides, insecticides and a plant growth regulator. The formerwere investigated in both soft and alcoholic beverages (mineral water, soda, juice, wine and beer)while agrochemicals were quantified in land cultivated vegetables, including mushroom, lettuce, alfalfasprout, cucumber, and celery.            Theparticularities of each investigated system and the differences in the correspondingdata treatment are presented and discussed.            The coupling of chromatographicapproaches with second-order chemometric calibration allows us to considerablysimplify the sample pretreatment and to significantly reduce the analysis time, resulting in analytical green methodsthat favorably compare with those usually employed in complex systemssuch as the ones here investigated. Low detection limits were achieved, even inthe presence of partially overlapped chromatographic and spectral bands amonganalytes and potential interferents. The detection capabilities allow one tomonitor the presence of the analytes in natural samples complying withinternational regulations.