Influence of the grain size on the quality of standardless WDXRF analysis of river Nile sediments

In multichannel wavelength-dispersive X-ray fluorescence spectrometry (WDXRF) the fluorescence intensity might depend on grain size and heterogeneity of the sample. Six river Nile sediment samples were collected two meters below the water surface from different locations covering the greater Cairo, Egypt. Each sample was dried at 65 °C for 48 h and divided into four grain size fractions: < 32 μm, 32–63 μm, 63–125 μm and 125–200 μm using different sieves. The dry sediment samples were mixed with low contamination binder (Wax, C₆H₈O₃N₂) in a mass ratio of wax:sample = 4:0.9 g. Sample pellets were made using a hydraulic press at a pelletizing pressure of 120 KN cm^{− 2}. The results show that the XRF intensities of the K_α radiation might increase or decrease with decreasing grain size, depending on the atomic number of the analyte. In the present thick pelletized samples, the penetration depth of the characteristic radiation increases at low grain sizes, and consequently the probability of the grain-size effect on the characteristic radiation decreases. Depending on the experimental data, a general theoretical equation, relating fluorescence intensity, grain size and atomic number, was derived by using cubic spline interpolation. The fractions were identified by WDXRF using standardless quantitative analysis, depending on the fundamental parameter approach. According to the present statistical analysis and the Certified Reference Material (CRM) results, the quantitative analysis results were found acceptable when the grain size of the river Nile sediments less than 32 μm. At a grain size > 63 μm, standardless analysis using fundamental parameter approach was found to be useful for qualitative and semi-quantitative analysis only whereas there are a strong positive correlations.