Calcium determination in biochar-based fertilizers by laser-induced breakdown spectroscopy using sodium as internal standard

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.