title: Partial least squares X-ray fluorescence determination of trace elements in sediments from the estuary of Nerbioi-Ibaizabal River.
abstract: The feasibility of partial least squares (PLS) regression modeling of X-ray fluorescence (XRF) spectra of estuarine sediments has been evaluated as a tool for rapid trace element content monitoring. Multivariate PLS calibration models were developed to predict the concentration of Al, As, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, V and Zn in sediments collected from different locations across the estuary of the Nerbioi-Ibaizabal River (Metropolitan Bilbao, Bay of Biscay, Basque Country). The study was carried out on a set of 116 sediment samples, previously lyophilized and sieved with a particle size lower than 63 microm. Sample reference data were obtained by inductively coupled plasma mass spectrometry. 34 samples were selected for building PLS models through a hierarchical cluster analysis. The remaining 82 samples were used as a test set to validate the models. Results obtained in the present study involved relative root mean square errors of prediction varying from 21%, for the determination of Pb at hundreds microg g(-1) level, up to 87%, for Ni determination at little tens microg g(-1) level. An average prediction error of +/-37% for the 14 elements under study was obtained, being in all cases mean differences between predicted and reference results of the same order than the standard deviation of three replicates from a same sample. Residual predictive deviation values obtained ranged from 1.1 to 3.9.
authors.affiliation: Department of Analytical Chemistry, Faculty of Sciences, University of Málaga, E29071 Málaga, Spain.
authors.forename: Javier
authors.initials: J
authors.lastname: Moros
authors.forename: Ainara
authors.initials: A
authors.lastname: Gredilla
authors.forename: Silvia
authors.initials: S
authors.lastname: Fdez-Ortiz de Vallejuelo
authors.forename: Alberto
authors.initials: A
authors.lastname: de Diego
authors.forename: Juan Manuel
authors.initials: JM
authors.lastname: Madariaga
authors.forename: Salvador
authors.initials: S
authors.lastname: Garrigues
authors.forename: Miguel
authors.initials: M
authors.lastname: de la Guardia
mesh_terms: D005618:Fresh Water / Q000737:chemistry*; D019015:Geologic Sediments / Q000737:chemistry*; D016018:Least-Squares Analysis; D013030:Spain; D013050:Spectrometry, Fluorescence / Q000379:methods*; D014131:Trace Elements / Q000032:analysis*
chemical_list: D014131:Trace Elements