Determination of trace elements in calcium rich carbonate rocks by Wavelength Dispersive X-ray Fluorescence Spectrometry for environmental and geological studies

A simple, rapid and non destructive Wavelength Dispersive X-ray Fluorescence Spectrometry (WDXRFS) was developed for the determination of trace elements such as V, Cr, Co, Ni, Cu, Zn, Pb, Ba, La, Ce, Nd, Rb, Sr, Y, Zr, and Nb in carbonate rocks with high calcium content. Samples of marble, limestone, fluorite ore and carbonatite-like rocks were chosen as objects under investigation. These samples have wide ranges of major and trace element contents, and high concentration of calcite (70-98%) in calcium rich carbonates. The sample mass required for infinite thickness was calculated for each element. In order to determine V, Cr, Co, Ni, Cu, Zn, Ba, La, Nd, Ce, sample weighting 1 g was pressed with a pressure of 100 kN. For the determination of Rb, Sr, Y, Zr, Nb, Pb, the sample mass was increased up to 5 g. The calibration curves were constructed by employing the International Certified reference materials (ICRMs) and in-house standard reference materials (HSRMs) of various types of rocks and sediments, and the matrix effects were taken into account using the influence coefficients (α-correction equations). Analytical figures of merit have also been assessed. The calculated values of the instrumental limit of the detection were within the interval from 0.5 to 4.0 mg kg−1. The repeatability and reproducibility were found to be satisfactory with the relative standard deviations lower than 5%. The accuracy was evaluated by the analysis of two reference materials and the comparison with the ICP-MS results. A good agreement was achieved between the reference and measured values with recoveries ranging from 85% to 115%. The relative disagreements between the XRF and ICP-MS results were less than 10%.