Determination of halogen levels in marine geological samples

Abstract

ABSTRACTA method for determining levels of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I) in marine geological samples using wavelength dispersive X-ray fluorescence is presented here. Samples are prepared as pressed powder pellets. The method makes full use of the advantages of the ability of the modern X-ray fluorescence spectrometer to detect ultra-light elements and high-powered X-rays. A series of calibration standards with an appropriate concentration range was developed using a standard addition method. Empirical coefficients were used to correct for matrix effects in the case of F and Cl, the rhodium Kα -Compton peak was used as internal standard for Br matrix corrections, and the rhodium Kb-Compton peak was used to correct for the matrix effect on I. For % concentration of the analyte, the precision (relative standard deviation) of the method was <5%. For concentrations <0.1%, the relative standard deviation depended heavily on the count rates (or concentration). The accuracy of the method was validated by comparison of the results to similar reference materials. The detection levels of this method (counting time100 s) were 100, 5, 0.5, and 10 µg g−1 for F, Cl, Br, and I, respectively. The method was here used to determine the levels of halogens in samples of 19 marine sediments (China, Russia, Canada, American), 10 marine manganese nodules (China, Russia, American, Germany, India, Japan), 4 cobalt-rich crust reference materials (Russia, China), reference materials, and 3 phosphorites.