Determination of concentrations of Sr and Ba in coal and coal combustion by-products: A comparison between results by ICP-MS and XRF techniques

Concentrations of trace elements in coal and coal combustion products are commonly analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) due to large number of elements detected and the relatively the low detection limits of this technique. Like other geological samples, complete dissolution of coal and coal combustion products is also essential for accurate ICP-MS results. In this study, Sr and Ba in coal and coal combustion products (fly and bottom ashes) from two coal-combustion power plants from North China analyzed by XRF and ICP-MS were comparatively studied. The concentrations of Sr and Ba analyzed by ICP-MS, when a mixture of acids (2 ml HF + 5 ml HNO3 for each 50 mg coal sample and 5 ml HF + 2 ml HNO3 for each 50 mg ash sample) was used for microwave-assisted digestion, do not fit well with the their relative XRF results. This is most probably due to the formation of the fluorides during microwave digestion, and this assumption is supported by the presence of various fluoride compounds, NaMgAl(F, OH)(6).H2O, NH4MgAlF6, AlF3, and K2SiF6, in the residues of all the coal and ash samples in our sequential extraction experiment. Cations of Sr and Ba were probably trapped into the divalent cation sites of the fluorides. Concentrations of Sr and Ba analyzed by ICP-MS using increased HF and HF/HNO3 ratio (7 ml HF and 2 ml HNO3 for each 50 mg coal/ash sample) are in better agreement with the XRF results. Our results indicate that excess amount of HF probably has led to the suppression of these elements due to fluoride precipitation. The results indicate that the modified digestion method is capable of achieving complete digestion of coal samples and results in a reliable analysis of Sr and Ba concentrations in coal samples and most fly ashes by ICP-MS. However, the formation of insoluble fluorides is probably not completely suppressed for some bottom ash samples, which can result in underestimation of Sr and Ba concentrations. Nevertheless, XRF analysis can serve as a reliable cross-check method to assist in the evaluation of the accuracy of ICP-MS results.