Over the years, laser-induced breakdown spectroscopy (LIBS) has been reported in the literature as an alternative to traditional methods of analysis, becoming well established among spectroanalytical techniques. LIBS is a technique widely used for qualitative approaches; however, it is necessary considerable effort for use in quantitative analysis, mainly due to severe matrix effects. These limitations make it difficult to broaden the application of LIBS in quantitative analysis. In this sense, this review discusses recent advances in calibration strategies applied in LIBS for minimizing matrix effects and enabling determination with satisfactory accuracy and precision. Applications, advantages, and limitations of the calibration strategies, such as matrix-matching calibration (MMC), internal standardization (IS), standard addition (SA), multi-energy calibration (MEC), one-point gravimetric standard addition (OP GSA), one-point and multi-line calibration (OP MLC), slope ratio calibration (SRC), two-point calibration transfer (TP CT), single-sample calibration (SSC), multiple linear regression (MLR), principal component regression (PCR), partial least squares (PLS) and artificial neural networks (ANN) are discussed.

This review attempts to present a broad view of the technique laser-induced breakdown spectroscopy (LIBS), since its origin, fundamentals, sample preparation strategies, use of chemometric tools for data processing, the advantages and limitations with regard to qualitative and quantitative analysis, aplications and future trends as an analytical technique that is in consolidation in analytical chemistry. LIBS is a rapid and versatile, which is able of providing qualitative and quantitative analytical information for practically any sample, in a virtually non-destructive way, without any substantial sample preparation. The instrumentation is simple, robust, compact, and enables remote analysis. The advancement of the LIBS applications in the areas of agriculture, environmental, food, biological/pharmaceutical, forensic, metallurgy and electronic waste were discussed in detail in this review. We consider that this review will be an important tool concerning dissemination of the LIBS, mainly for audience of undergraduate courses, and disciplines related to instrumental analysis.

This study describes the application of laser-induced breakdown spectroscopy (LIBS) for the direct determination of Ca, K and Mg in powdered dietary supplements. Multi-energy calibration (MEC) method was applied to obtain a calibration curve. With MEC, it was possible to observe spectral interferences and select adequate emission lines from LIBS. For Ca and Mg, five lines were selected and for K just two lines among four could be selected (compromising the results). The trueness for dietary supplements ranged from 81 to 103% for Ca and 74 to 106% for Mg. For K, just the samples S3 (95%) and S5 (109%) showed acceptable trueness values. In the case of Ca and K, besides the MEC, the normalization using C as internal standard also improved the figure of merit results. The MEC and normalization processes showed that possible matrix effect and spectral interferences could be avoided, and the results of trueness and precision were satisfactory.

In this study, two laser-based techniques, laser-induced breakdown spectroscopy (LIBS) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) were used for analytical signal evaluation of Ti, Al, and V and investigation of possible harmful elements eventually present as minor elements in Ti alloys. Due to the lack of certified reference materials, samples were also analyzed by wavelength dispersive X-ray fluorescence (WDXRF) and inductively coupled plasma optical emission spectrometry (ICP OES) after microwave-assisted digestion. To maximize the efficiency of LIBS and LA-ICP-MS, operational conditions were adjusted aiming to find optimal analytical performance. LIBS showed several Ti emission lines and few signals for Al and V. LA-ICP-MS was able to detect all three major constituents. For quantitative analysis, the correlation of intensity signals from LIBS analysis with reference values obtained by ICP OES was not successful, showing that there are still difficulties for quantification using solid samples. Measurements using ICP OES showed that additionally to major constituents, only Fe was present in concentrations around 0.2%. Analysis by WDXRF confirmed the presence of Fe. Results using both methods, i.e., ICP OES and WDXRF, were in good agreement.