Development of a species-specific isotope dilution GC-ICP-MS method for the determination of thiophene derivates in petroleum products

Heilmann, Jens; Heumann, Klaus G.
January 2008
Analytical & Bioanalytical Chemistry;Jan2008, Vol. 390 Issue 2, p643
Academic Journal
A species-specific isotope dilution technique for accurate determination of sulfur species in low- and high-boiling petroleum products was developed by coupling capillary gas chromatography with quadrupole ICP-MS (GC-ICP-IDMS). For the isotope dilution step 34S-labeled thiophene, dibenzothiophene, and mixed dibenzothiophene/4-methyldibenzothiophene spike compounds were synthesized on the milligram scale from elemental 34S-enriched sulfur. Thiophene was determined in gasoline, ‘sulfur-free’ gasoline, and naphtha. By analyzing reference material NIST SRM 2296, the accuracy of species-specific GC-ICP-IDMS was demonstrated by an excellent agreement with the certified value. The detection limit is always limited by the background noise of the isotope chromatograms and was determined for thiophene to be 7 pg absolute, which corresponds to 7 ng sulfur/g sample under the experimental conditions used. Dibenzothiophene and 4-methyldibenzothiophene were determined in different high-boiling petroleum products like gas oil, diesel fuel, and heating oil. In this case a large concentration range from about < 0.04 to more than 2,000 μg g−1 was covered for both sulfur species. By parallel GC-ICP-MS and GC-EI-MS experiments (EI-MS electron impact ionization mass spectrometry) the substantial influence of co-eluting hydrocarbons on the ICP-MS sulfur signal was demonstrated, which can significantly affect results obtained by external calibration but not those by the isotope dilution technique.


Related Articles

  • Isotope dilution analysis for speciation. Ruiz Encinar, Jorge // Analytical & Bioanalytical Chemistry;Jan2003, Vol. 375 Issue 1, p41 

    The article presents information about isotope dilution analysis for speciation. The use of compounds isotopic ally labelled with D and/or 13C has been widespread in organic chemistry during the last 25 years but it was only few years ago, coinciding with the inductively coupled plasma mass...

  • The role of sulfur and sulfur isotope dilution analysis in quantitative protein analysis. Rappel, Christina; Schaumlöffel, Dirk // Analytical & Bioanalytical Chemistry;Jan2008, Vol. 390 Issue 2, p605 

    The element sulfur is almost omnipresent in all natural proteomes and plays a key role in protein quantification. Incorporated in the amino acids cysteine and methionine, it has been served as target for many protein-labeling reactions in classic quantitative proteomic approaches based on...

  • Ultratrace-level radium-226 determination in seawater samples by isotope dilution inductively coupled plasma mass spectrometry. Varga, Zsolt // Analytical & Bioanalytical Chemistry;Jan2008, Vol. 390 Issue 2, p511 

    An improved and novel sample preparation method for 226Ra determination in liquid samples by isotope dilution inductively coupled plasma sector field mass spectrometry using laboratory-prepared 228Ra tracer has been developed. The procedure involves a selective preconcentration achieved by...

  • On-line species-unspecific isotope dilution analysis in the picomolar range reveals the time- and species-depending mercury uptake in human astrocytes. Wehe, Christoph; Pieper, Imke; Holtkamp, Michael; Thyssen, Georgina; Sperling, Michael; Schwerdtle, Tanja; Karst, Uwe // Analytical & Bioanalytical Chemistry;Mar2014, Vol. 406 Issue 7, p1909 

    In order to reveal the time-depending mercury species uptake by human astrocytes, a novel approach for total mercury analysis is presented, which uses an accelerated sample introduction system combined on-line with an inductively coupled plasma mass spectrometer equipped with a...

  • Isotopic analyses by ICP-MS in clinical samples. Rodushkin, Ilia; Engström, Emma; Baxter, Douglas // Analytical & Bioanalytical Chemistry;Mar2013, Vol. 405 Issue 9, p2785 

    This critical review focuses on inductively coupled plasma mass spectrometry (ICP-MS) based applications for isotope abundance ratio measurements in various clinical samples relevant to monitoring occupational or environmental exposure, human provenancing and reconstruction of migration pathways...

  • Mercury speciation analysis in human hair by species-specific isotope-dilution using GC-ICP-MS. Laffont, Laure; Maurice, Laurence; Amouroux, David; Navarro, Patricia; Monperrus, Mathilde; Sonke, Jeroen; Behra, Philippe // Analytical & Bioanalytical Chemistry;Mar2013, Vol. 405 Issue 9, p3001 

    We optimized a mercury (Hg) speciation extraction method for human hair in combination with species-specific isotope-dilution analysis by gas chromatography-inductively coupled plasma-mass spectrometry (GC-ICP-MS). The method was validated on human hair reference material RM (IAEA-086), which is...

  • Quantification of Fe atoms by MC-ICP-MS for the redetermination of the half-life. Kivel, Niko; Schumann, Dorothea; Günther-Leopold, Ines // Analytical & Bioanalytical Chemistry;Mar2013, Vol. 405 Issue 9, p2965 

    In many scientific fields, the half-life of radionuclides plays an important role. The accurate knowledge of this parameter has direct impact on, e.g., age determination of archeological artifacts and of the elemental synthesis in the universe. In order to derive the half-life of a long-lived...

  • Dissolution and assay of neptunium oxide. Xu, N.; Tandon, L.; Gallimore, D.; Lujan, E.; Porterfield, D.; Colletti, L.; Kuhn, K. // Journal of Radioanalytical & Nuclear Chemistry;Apr2013, Vol. 296 Issue 1, p245 

    A case study for dissolution and assay of neptunium oxide is presented in this paper. A simple analytical method for completely dissolving neptunium oxide is described. Addition of 12 M HNO is sufficient to dissolve neptunium oxide without precipitate formation. Various analytical chemistry...

  • Femtosecond laser ablation inductively coupled plasma mass spectrometry: achievements and remaining problems. Koch, J.; Günther, D. // Analytical & Bioanalytical Chemistry;Jan2007, Vol. 387 Issue 1, p149 

    The article presents the role of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), the most versatile method for analyzing solid material. The examining of diversified operational parameters including laser wavelength, pulse duration, carrier gas and others for specifying...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics