title: In situ sulfur isotopes (δ(34)S and δ(33)S) analyses in sulfides and elemental sulfur using high sensitivity cones combined with the addition of nitrogen by laser ablation MC-ICP-MS.
abstract: The sulfur isotope is an important geochemical tracer in diverse fields of geosciences. In this study, the effects of three different cone combinations with the addition of N2 on the performance of in situ S isotope analyses were investigated in detail. The signal intensities of S isotopes were improved by a factor of 2.3 and 3.6 using the X skimmer cone combined with the standard sample cone or the Jet sample cone, respectively, compared with the standard arrangement (H skimmer cone combined with the standard sample cone). This signal enhancement is important for the improvement of the precision and accuracy of in situ S isotope analysis at high spatial resolution. Different cone combinations have a significant effect on the mass bias and mass bias stability for S isotopes. Poor precisions of S isotope ratios were obtained using the Jet and X cones combination at their corresponding optimum makeup gas flow when using Ar plasma only. The addition of 4-8 ml min(-1) nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to significantly enlarge the mass bias stability zone at their corresponding optimum makeup gas flow in these three different cone combinations. The polyatomic interferences of OO, SH, OOH were also significantly reduced, and the interference free plateaus of sulfur isotopes became broader and flatter in the nitrogen mode (N2 = 4 ml min(-1)). However, the signal intensity of S was not increased by the addition of nitrogen in this study. The laser fluence and ablation mode had significant effects on sulfur isotope fractionation during the analysis of sulfides and elemental sulfur by laser ablation MC-ICP-MS. The matrix effect among different sulfides and elemental sulfur was observed, but could be significantly reduced by line scan ablation in preference to single spot ablation under the optimized fluence. It is recommended that the d90 values of the particles in pressed powder pellets for accurate and precise S isotope analysis should be less than 10 μm. Under the selected optimized analytical conditions, excellent agreements between the determined values and the reference values were achieved for the IAEA-S series standard reference materials and a set of six well-characterized, isotopic homogeneous sulfide standards (PPP-1, MoS2, MASS-1, P-GBW07267, P-GBW07268, P-GBW07270), validating the capability of the developed method for providing high-quality in situ S isotope data in sulfides and elemental sulfur.
authors.affiliation: State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, PR China.
authors.forename: Jiali
authors.initials: J
authors.lastname: Fu
authors.affiliation: State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, PR China; The Beijing SHRIMP Center, Institute of Geology, Chinese Academy of Geological Sciences, Beijing 102206, PR China. Electronic address: zchu@vip.sina.com.
authors.forename: Zhaochu
authors.initials: Z
authors.lastname: Hu
authors.affiliation: State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, PR China.
authors.forename: Wen
authors.initials: W
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, PR China; National Research Council Canada, 1200 Montreal Rd., Ottawa, Ontario K1A 0R6, Canada.
authors.forename: Lu
authors.initials: L
authors.lastname: Yang
authors.affiliation: State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, PR China.
authors.forename: Yongsheng
authors.initials: Y
authors.lastname: Liu
authors.affiliation: State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, PR China.
authors.forename: Ming
authors.initials: M
authors.lastname: Li
authors.affiliation: State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, PR China.
authors.forename: Keqing
authors.initials: K
authors.lastname: Zong
authors.affiliation: State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, PR China.
authors.forename: Shan
authors.initials: S
authors.lastname: Gao
authors.affiliation: State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, PR China.
authors.forename: Shenghong
authors.initials: S
authors.lastname: Hu
keywords: LA-MC-ICP-MS; Matrix effect; Nitrogen; Oxide and hydride interference reduction; Sulfide reference materials; Sulfur isotope