High precision in-situ Pb isotopic analysis of sulfide minerals by femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry

An in-situ microanalysis of Pb isotopic compositions in sulfide minerals is carried out by using femtosecond laser-ablation multi-collector inductively coupled plasma mass spectrometry (fsLA-MC-ICP-MS). High-temperature-activated carbon was used to filter Hg contained in the carrier gas, which reduced the Hg background signal by 48% and also lowered the detection limit of the analysis. Fractionation and mass discrimination effects existing in the ICP-MS analytical processes were corrected using an internal reference Tl in conjunction with an external reference NIST SRM 610. The proposed method was used to analyze the Pb isotopic compositions of chalcopyrite, pyrite, and sphalerite from the Dulong Sn-Zn-In polymetallic ore district. The results showed that in this ore district, the sulfide minerals and different grains of the same sulfide mineral show a large variation in Pb content up to 1000-fold. The studied pyrites show relatively higher Pb contents and homogeneous Pb isotopic compositions, whereas the sphalerites have low Pb contents but most variable Pb isotopic compositions. It is suggested that the large variation of Pb isotopic composition may reflect a late hydrothermal superimposition on the primary sulfide formation. In addition, radiogenic Pb accumulated by radioactive decay of trace amounts of U over time in the host minerals may also be one of the causes for the large variation range of Pb content and Pb isotopic composition of those low-Pb sphalerites. Chalcopyrite and sphalerite grains with Pb content greater than 10 ppm presented a consistent Pb isotopic distribution, whereas all the sulfide grains with Pb content greater than 100 ppm had consistent Pb isotopic composition within 2s measurement uncertainties. The in-situ analysis of Pb isotopic composition agreed well with the results obtained by conventional chemical methods within 2s measurement uncertainties, indicating that the data obtained by fsLA-MC-ICP-MS are reliable. Additionally, this study indicates that the Pb isotopic composition could truthfully record the source of ore-forming minerals only for sulfide minerals with high Pb content. On the contrary, the Pb isotopic composition of low-Pb sulfide minerals may be affected by trace amounts of U in the host minerals that may lead to a highly radiogenic Pb isotope ratio. Alternatively, it is also possible that late fluid metasomatic overprinting may alter the Pb isotopic compositions.