Determination of bromine, chlorine, fluorine, phosphorus and sulfur in soil and stream sediment by wavelength dispersive X-ray fluorescence spectrometry with pressed powder pellet
ZHAO Wenzhi1, ZHANG Tianhao2,3, LU Bing1, LÜ Shengnan1
1. Center for Harbin Natural Resources Comprehensive Survey, China Geological Survey, Harbin 150039, China; 2. College of Engineering and Applied Science, Nanjing University, Nanjing 210023, China; 3. College of Chemical and Biological Engineering, Nantong Vocational University, Nantong 226007, China
Abstract：When the contents of bromine, chlorine, fluorine, phosphorus and sulfur in soil and stream sediment are determined simultaneously by wavelength dispersive X-ray fluorescence spectrometry(WD-XRF) with direct pressed powder pellet method, these five elements will be affected by mineral, chemical state and particle size effect. Therefore, the determination difficulty is relatively high. In experiments, the certified reference materials of stream sediment and soil were selected to establish the calibration curve. The empirical coefficient method and Rh Kα Compton scattering internal standard method were used to correct the matrix effect and spectral line interference during the determination of Br. The empirical coefficient method and F background internal standard method were used for correction during the determination of F. The testing of Cl, P and S could be corrected by empirical coefficient method. Consequently, the accurate determination of five elements were realized. It was found that the testing value of Cl increased with the number of repeated detections. When the Cl content was up to 4 800 μg/g, the measured value was not affected by the number of measurements. In order to ensure the accuracy of the analysis results, the sample could only be measured once, and the first measurement result shall prevail. Moreover, the sample should be measured in time or placed in a desiccator for testing. In addition, the influence of valence state on the fluorescence intensity of S was not the main factor, while the mineral effect chemical state and particle size effect were possibly the most important interference factors. It was confirmed that As Kβ line overlapped with Br Kα line, Mo Lγ1 line overlapped with Cl Kα line, Mo Lα line overlapped with S Kα line, and Y Lβ1 line overlapped with P Kα line. The interference was corrected by empirical coefficients. Five elements in the certified reference materials of stream sediment and soil were determined. The relative errors (RE) of determination results were all less than 11%, and the relative standard deviations (RSD) were less than 6%. The limit of detection and accuracy could meet the requirements of industrial standard (DZ/T 0258-2014). The proposed method was suitable for measuring large quantities of geological samples.
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