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.

IWDTF; LIBS; Animal manure composts; Cu; Zn;HEAVY-METAL CONTENTS; MULTIELEMENT ANALYSIS; ACCURACY IMPROVEMENT; MINERAL FERTILIZERS; LIVESTOCK FEEDS; TRACE-ELEMENTS; SPECTROMETRY; LIBS; CONTAMINANTS; TRANSFORM

Spectral denoising offers a basis for effective and accurate quantitative modeling of laser-induced breakdown spectroscopy (LIBS). To provide a solution for the defects of the traditional hard threshold function (HTF) and the soft threshold function (STF) for wavelet denoising methods, an improved wavelet dual threshold function (IWDTF) has been developed. Simulation analyses proved that the IWDTF could provide abetter denoising performance than the traditional functions. The IWDTF was applied to LIBS denoising and quantitative modeling of the Cu and Zn contents in representative Chinese aerobic composting samples. The results showed that the best spectral denoising effects for the Cu and Zn models were achieved when the adjustment parameters k(0), a, and theta were 0.9, 0.7 x lambda(1), and 0.1 x pi, and 0.2, 0.2 x lambda(1), and 0.1 x pi, respectively, and corresponding models' performances for Cu and Zn were both greatly improved, yielding R-p(2) of 0.9807 and 0.9177, RMSEP of 67.49 mg/kg and 84.92 mg/kg, and RPD of 3.12 and 3.07, respectively. (C) 2017 Published by Elsevier B.V.

Biochar-based fertilizers; Calcium; Libs; Internal standardization;SPECTROMETRY; SOILS; COAL

Biochar has gained agricultural importance as a soil amendment because of its important agricultural properties such as water retention, plant nutrient supplier, promoter of microorganism growth, sequestration action of atmospheric CO2, etc. Further, it is a low cost material being produced by recycling. Due to its active sites, biochar can adsorb nutrients so acting as a soil fertilizer. Thus the rapid assessment of nutrients in these materials is essential to ensure quality control for agricultural purposes. This work aimed to develop a simple analytical method based on Laser-Induced Breakdown Spectroscopy (LIBS) to determine Ca in biochar-based fertilizers. In particular, biochar samples enriched with Ca were prepared from peanut shells, residues of eucalyptus and banana fibers. The calibration standards were prepared by matrix matching using a biochar from eucalyptus residues. Different spectral preprocessing were evaluated to enhance the precision and accuracy of the method. However, the matrix effects demanded the use of internal standardization as the appropriate methodology to obtain the best accuracy. A linear correlation coefficient of 0.989 and a linear work range of 1.51-11.23% Ca were obtained using the proposed method, which yielded limits of detection and quantification of 0.45% e 1.51%, respectively. Calcium contents determined by LIBS in biochar-based fertilizers were in good agreement (paired t-test at 95% confidence level) with those determined by using High-Resolution Continuous Source Atomic Absorption Spectrometry (HR-CS FAAS) as the reference technique. Thus, the importance of internal standardization was demonstrated to be successful for the quantitative analysis of Ca in complex matrices like biochar-based fertilizers. (C) 2017 Elsevier B.V. All rights reserved.

Laser induced breakdown spectrometry; Partial Least Squares; PZT ceramics; Calibration strategies;ATOMIC EMISSION-SPECTROMETRY; ABSORPTION-SPECTROMETRY; CLASSIFICATION; CHEMOMETRICS

In PZT (Lead Zirconate Titanate) ceramics, stoichiometric composition is closely related with physical properties and applications. Laser-induced BreakdownSpectroscopy (LIBS) have shown to be a suitable technique for analyzing many types of solid samples, usually in combination with multivariate techniques. In this study, a method for quick determination of Pb, Zr, Ti and Sr in PZT ceramics using LIBS was proposed. Spectral data is analyzed with PLS (Partial Least Squares), providing results better than Multiple Linear Regression (MLR) and external calibration, when compared with previous determination of the same group of ceramics by PIXE (Particle Induced X-ray Emission). Most of predicted individual concentrations were between 98 and 102% of the reference value for Pb, and between 90 and 110% for the rest of the elements. (C) 2016 Elsevier B.V. All rights reserved.

Soil; Plant; Fertilizer; DP LIBS analysis; Orthogonal geometry; Ablative energy;SIGNAL ENHANCEMENT; PLANT MATERIALS; PLASMA; LIBS; FERTILIZERS; ABLATION; SOILS; QUANTIFICATION; CONTAMINANTS; DEPENDENCE

A soil, a plant and a fertilizer sample were investigated by double-pulse (DP) laser-induced breakdown spectroscopy (LIBS) in orthogonal beam geometry using a reheating configuration. The DP-LIBS signal enhancement was evaluated with respect to the corresponding single-pulse (SP) LIBS as a function of the interpulse delay at various ablation energies. The maximum signal enhancement measured was 155-fold when low ablation energy (4 mJ) and an interpulse delay of 10 mu s were used. At high laser energies (>= 16 mJ) and interpulse delay of 0.6 mu s, the maximum signal enhancement was up to 3-fold. The effect of excitation energies and interpulse delays on emission line intensities was discussed in the various conditions used. The emission line enhancement measured for ionic lines was always higher than that of atomic lines. Plasma excitation temperature and electron density measured as a function of interpulse delays at various ablation energies were shown to be related to the emission line intensities. (C) 2017 Elsevier B.V. All rights reserved.