Quantitative differentiation of sulfur in different oxidation states (-II and +VI) by WD-XRF

Sulfur is one of the most abundant non-metals in the Earth’s crust and a key component of sulfidic ores. A number of methods for the determination of the total sulfur content in geochemical samples are available in the literature. However, sulfur appears in numerous oxidation states. Sulfide (-II) and sulfate (+VI) are the most common ones, but options for a analytical chemical differentiation between them are quite limited. This distinction could be achieved by combustion with stepwise adjustable decomposition temperatures (Brumsack 1981) or by classical wet-chemical methods (e.g., Kokkonen et al. 1987), but these methods require special efforts and can not be implemented during high throughput routine analyses.
Selective separation of different oxidation states by WD-XRF has been reported for sulfur (Perino et al. 2002), aluminium and silicon (Perino et al. 2002), iron (Finkelshtein and Chubarov 2010), and chromium (Malherbe and Claverie 2013). Referring to these known methods, two techniques for the quantitative differentiation between the most common sulfur species were developed, respectively improved that are based on a routine WD-XRF measurement. The first method is predicated on the exact position of the Kα1,2 peak in the XRF spectra, depending on the sulfide and sulfate content. The second option is based on the Kβ’/Kβ-ratio. As opposed to sulfides, sulfates show a Kβ’ satellite peak and its area and height depend on the sulfate concentration.
Both methods provide simple and time-saving options to differentiate between sulfide and sulfate, because the separation of the different oxidation states can be done during a routine WD-XRF measurement without any special efforts. Furthermore, samples with high amounts of fluorine, which could cause damages of technical devices, can be measured without any problems in the vacuum of the spectrometer. We aware that our research results may have two limitations. The first relates to the sulfur content. The method can not be used for samples with concentrations of the sulfatic and/or sulfatic component smaller than 10 g kg-1. The second one is the overlap of the lead (Pb) Mβ peak and the sulfur Kβ’ satellite peak. Samples with detectable lead amounts can only be investigated by the so-called Kα method.
We are currently in the process of a validation of our results by a second, independent method to further advance our investigations. Samples from Saxon mining dump drill holes appear suitable. Their total sulfur content and sulfide and sulfate concentration vary with depth. Suitable applications of these techniques are the high throughput routine analyses of samples that contain or consist of sulfidic ores.
References
Brumsack, H.-J., 1981. A Simple Method for the Determination of Sulfide- and Sulfate-Sulfur in Geological Materials by Using Different Temperatures of Decomposition. Fresenius' Journal of Analytical Chemistry, 307, 206.
Finkelshtein, A.L. and Chubarov, V.M., 2010. X-ray fluorescence determination of the FeO/Fe2O3tot ratio in igneous rocks. X-Ray Spectrometry, 39 (1), 17–21.
Kokkonen, P., Palko, M., and Lajunen, Lauri H. J., 1987. Indirect determination of sulfate and sulfide by flame atomic absorption spectrometry. Atomic Spectroscopy, 8 (3), 98–100.
Malherbe, J. and Claverie, F., 2013. Toward chromium speciation in solids using wavelength dispersive X-ray fluorescence spectrometry Cr Kbeta lines. Analytica Chimica Acta (773), 37–44.
Perino, E., et al., 2002. Determination of oxidation states of aluminium, silicon and sulfur. X-Ray Spectrometry, 31 (2), 115–119.