Determination of sulfur in fossil fuels by isotope dilution electrothermalvaporization inductively coupled plasma mass spectrometry

The determination of S by solution nebulization quadrupole inductively coup led plasma mass spectrometry (ICP-MS) is difficult because of interferences from oxygen dimer ions. The large O-16(2)+ ion current from the solvent wa ter is a serious interference at S-32, the most abundant of the four isotop es, and precludes its measurement. The isotopic composition of S varies in nature as a consequence of natural mass fractionation; therefore, high accu racy isotope dilution mass spectrometric (IDMS) determination of sulfur req uires that the ratio of S-32/S-34 be measured, for the two isotopes represe nt over 99% of natural sulfur. In this work, electrothermal vaporization wa s used to generate a water-free aerosol of the sample. Non-solvent sources of oxygen were investigated and the spectral background minimized. Further reduction of the oxygen dimer was achieved by using nitrogen as an oxygen-s cavenger in the argon plasma. The isotope ratio of S-32/S-34 was used for t he determination of S by IDMS. The repeatability of the S-32/S-34 ratio in terms of the relative standard error (95% confidence level) of 6 replicate measurements of the spiked and the unspiked samples was about 0.3% and 0.7% , respectively. The detection limit of the method was 4 epsilon ng epsilong (-1). Sulfur in two fossil fuel reference materials was measured and the re sults were in good agreement (within 0.3%) with those obtained by the more precise thermal ionization mass spectrometry (TIMS) method.