title: Isotope dilution ICP-MS with laser-assisted sample introduction for direct determination of sulfur in petroleum products.
abstract: Inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with direct laser-assisted introduction of isotope-diluted samples into the plasma, using a laser ablation system with high ablation rates, was developed for accurate sulfur determinations in different petroleum products such as 'sulfur-free' premium gasoline, diesel fuel, and heating oil. Two certified gas oil reference materials were analyzed for method validation. Two different 34S-enriched spike compounds, namely, elementary sulfur dissolved in xylene and dibenzothiophene in hexane, were synthesized and tested for their usefulness in this isotope dilution technique. The isotope-diluted sample was adsorbed on a filter-paper-like material, which was fixed in a special holder for irradiation by the laser beam. Under these conditions no time-dependent spike/analyte fractionation was only observed for the dibenzothiophene spike during the laser ablation process, which means that the measured 34S/32S isotope ratio of the isotope-diluted sample remained constant-a necessary precondition for accurate results with the isotope dilution technique. A comparison of LA-ICP-IDMS results with the certified values of the gas oil reference materials and with results obtained from ICP-IDMS analyses with wet sample digestion demonstrated the accuracy of the new LA-ICP-IDMS method in the concentration range of 9.2 microg g(-1) ('sulfur-free' premium gasoline) to 10.4 mg g(-1) (gas oil reference material BCR 107). The detection limit for sulfur by LA-ICP-IDMS is 0.04 microg g(-1) and the analysis time is only about 10 min, which therefore also qualifies this method for accurate determinations of low sulfur contents in petroleum products on a routine level.
authors.affiliation: Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55099 Mainz, Germany.
authors.forename: Sergei F
authors.initials: SF
authors.lastname: Boulyga
authors.forename: Jens
authors.initials: J
authors.lastname: Heilmann
authors.forename: Klaus G
authors.initials: KG
authors.lastname: Heumann
mesh_terms: D007834:Lasers; D013058:Mass Spectrometry / Q000295:instrumentation / Q000379:methods; D015394:Molecular Structure; D010578:Petroleum / Q000032:analysis*; D011865:Radioisotope Dilution Technique; D013455:Sulfur / Q000032:analysis* / Q000737:chemistry
chemical_list: D010578:Petroleum; D013455:Sulfur