Portable laser-induced breakdown spectroscopy (LIES); Chemometric analysis; Hazardous elements (HEs); Suspended particulates matter (SPM); Storm event;SURFACE BOTTOM SEDIMENTS; SPECTROSCOPY; CALCIUM; FLUXES; METALS; LIBS
The main objective of this work is to provide researchers with a fast methodology of analysis capable to assess water quality in an urban river catchment during extreme rainfall events without previous elemental quantification. The analytical methodology combines measurement with portable laser-induced breakdown spectroscopy (LIBS) and direct chemometric treatment of the LIBS spectra. With this aim, suspended particular matter (SPM) samples were collected during five storm events, every 2 h with an automatic water sampler in three control points (gauging stations) of an urban river (Deba River, Basque Country, Spain). SPM samples were analyzed in situ by a handheld laser induced breakdown spectrometry (HH-LIBS), and the complete LIBS spectra were statistically analyzed by Principal Component Analysis (PCA) after outlier identification by k-nearest neighbors (kNN). The PCA results showed differentiation between monitored localizations and the period when the storm event occurred. It was also possible to identify important discriminant variables, some of them corresponding to hazardous elements such as Pb, Cr, Ni, and Cu. Basing on the correlation between variables, it was possible to identify their sources (urban/municipal contamination, anthropogenic activities, etc.). Moreover, thanks to this methodology, it was possible to predict the mobilization of hazardous elements at the end of a storm event and determine the environmental risk assessment in an urban river.