laser-induced breakdown spectroscopy; phosphate rocks; organomineral fertilizers; principal components analysis; partial least squares regression;ELEMENTAL ANALYSIS; PLANT MATERIALS; SOIL; CHEMOMETRICS

A number of phosphate rocks and organomineral P fertilizers was analyzed comparatively by laser-induced breakdown spectroscopy (LIBS) in both single- and double-pulse modes associated with two chemometric methods, i.e., principal components analysis (PCA) and partial least squares regression (PLSR). PCA was demonstrated to be a valuable method for the identification of spectral differences between similar samples with only minor compositional differences. The raw and normalized LIBS spectra were able to provide effective identification and discrimination at a 95% confidence level and in good agreement with the reference concentrations. Results obtained confirm the promising potential of LIBS for the rapid classification of P fertilizers in situ.

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.

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.

SOILS; AGE; LIBS

Laser-induced breakdown spectroscopy (LIBS) is showing to be a promising, quick, accurate, and practical technique to detect and measure metal contaminants and nutrients in urban wastes and landfill leachates. Although conventional LIBS presents some limitations, such as low sensitivity, when used in the single pulse configuration if compared to other spectroscopic techniques, the use of the double-pulse (DP) configuration represents an adequate alternative. In this work DP LIBS has been applied to the qualitative and quantitative analysis of mercury (Hg) in landfill leachates. The correlation analysis performed between each intensified charge-coupled device pixel and the Hg concentration allowed us to choose the most appropriate Hg emission line to be used for its measure. The normalization process applied to LIBS spectra to correct physical matrix effects and small fluctuations increased from 0.82 to 0.98 the linear correlation of the calibration curve between LIBS and the reference data. The limit of detection for Hg estimated using DP LIBS was 76 mg Kg(-1). The cross validation (leave-one-out) analysis yielded an absolute average error of about 21%. These values showed that the calibration models were close to the optimization limit and satisfactory for Hg quantification in landfill leachate. (C) 2017 Optical Society of America

SIGNAL ENHANCEMENT; LIBS; DEPENDENCE; SOIL; MICROANALYSIS; EMISSION; ABLATION; LIQUIDS

Laser-induced breakdown spectroscopy (LIBS) is a technique increasingly used to perform fast semi-quantitative multi-elemental analyses of various materials without any complex sample preparation, being also suitable for in situ analyses. Few studies have been performed to understand the influence of laserwavelength on LIBS analytical performance on environmental samples. The main goal of this study was to perform a comparative elemental analysis of a number of soils, citrus leaves, and synthetic solid matrices using two different wavelengths, i.e., 532 and 1064 nm of Nd: YAG lasers, and a spectrometer coupled to a non-intensified charge-coupled device camera as the detection system. The emission lines with higher upper energy level, i.e., C I-193.03 (7.685 eV) and Si I-212.41 nm (6.616 eV), were more intense when using the 532 nm than the 1064 nm laser light, whereas the opposite occurred for elements with lower upper energy level, i.e., Ti I-336.12 nm (3.716 eV) and Fe I-368.75 nm (4.220 eV). The observed increase in LIBS signal between the two wavelengths is about 30-50%. The relationship between the line emission intensities and the used excitation wavelengths were associated to the upper level energy of the element.