Spectral fitting approach for the determination of enrichment and contamination factors in mining sediments using laser-induced breakdown spectroscopy

Monitoring of pollution index values in sediments is crucial in assessing the environmental impacts of toxic metals in a given location. These indices are typically acquired using elaborate and tedious calibration curve-dependent techniques such as (inductively coupled plasma – optical emission spectroscopy) ICP-OES and (atomic absorption spectroscopy) AAS. In this study, laser-induced breakdown spectroscopy (LIBS) was used as a simple and fast alternative method for estimating enrichment factor (EF) and contamination factor (CF) of the sediment samples obtained from selected mining sites. Quantitative analyses of three metal targets (Cd, Pb, and Zn) were done using a calibration-free LIBS method based on the Boltzmann population distribution. Both the EF and CF values calculated from classical ICP-OES method provided significantly high correspondence with the respective EF (R² = 0.8862–0.9770, p < 0.01–0.05) and CF (R² = 0.9454–0.9714, p < 0.01) obtained from the developed LIBS method. The intensity-based LIBS approach identified samples AC2 and CCC as the ones with the highest and lowest pollution index values, respectively. The same observation was seen using the concentration-based ICP-OES technique which showed good correlation between the two methods. The correlation results showed the potential of the curve-fitting LIBS analysis in evaluating the level of metal contamination in an area without the preparation of matrix-matched calibration curves.