Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS
Craddock, Paul R.
Rouxel, Olivier J.
Ball, Lary A.
MetadataShow full item record
We have developed a technique for the accurate and precise determination of 34S/32S isotope ratios (δ34S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O2+. Standard–sample bracketing is used to correct for the instrumental mass bias of unknown samples. Blanks on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.
Author Posting. © Elsevier B.V. , 2008. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Chemical Geology 253 (2008): 102-113, doi:10.1016/j.chemgeo.2008.04.017.
Showing items related by title, author, creator and subject.
Tostevin, Rosalie; Turchyn, Alexandra V.; Farquhar, James; Johnston, David T.; Eldridge, Daniel L.; Bishop, James K. B.; McIlvin, Matthew R. (Elsevier, 2014-04-16)We present 28 multiple sulfur isotope measurements of seawater sulfate (δ34SSO4δ34SSO4 and Δ33SSO4Δ33SSO4) from the modern ocean over a range of water depths and sites along the eastern margin of the Pacific Ocean. The ...
Sulfur isotope evidence for microbial sulfate reduction in altered oceanic basalts at ODP Site 801 Rouxel, Olivier J.; Ono, Shuhei; Alt, Jeffrey C.; Rumble, Douglas; Ludden, John (2008-01-08)The subsurface biosphere in the basaltic ocean crust is potentially of major importance in affecting chemical exchange between the ocean and lithosphere. Alteration of the oceanic crust commonly yields secondary pyrite ...
Friedman, Carrie T. (Massachusetts Institute of Technology and Woods Hole Oceanographic Institution, 1998-02)Stable sulfur isotopes (δ34S) and trace Co are analyzed in sulfide and sulfate minerals from six sample types collected from the TAG active mound, 26°N Mid-Atlantic Ridge. δ34S values range from 2.7 to 2O.9%, with sulfate ...