Non-matrix-matched determination of lead isotope ratios in ancient bronze artifacts by femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry

Abstract

In this study, lead isotopic ratios in bronze artifacts were non-matrix-matched determined directly by femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (fsLA-MC-ICP-MS). We evaluated the necessity of matrix matching for lead isotope ratio analyses of bronzes by adopting thallium solution to correct mass discrimination during mass spectrometer measurements. Lead isotope ratios of four bronze reference materials were measured by fsLA-MC-ICP-MS to determine the quality of data when calibrating samples with standards having different physical characteristics and chemical compositions. The average 206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb, 207Pb/206Pb and 208Pb/206Pb ratios determined by fsLA-MC-ICP-MS were within 0.06% of that by solution nebulizer MC-ICP-MS (SN-MC-ICP-MS). The results indicate that accurate lead isotopic compositions could be obtained by fsLA-MC-ICP-MS technique after non-matrix-matched standards calibration. Additionally, the lead isotopic compositions are presented for five Chinese bronze reference materials using fsLA-MC-ICP-MS. Homogeneity of lead isotope distribution was expressed as the RSD range from 0.010% to 0.017% for 208Pb/204Pb, 207Pb/204Pb, 206Pb/204Pb ratios. Therefore, the five bronze materials could potentially serve as external calibration standards and quality control samples for in situ lead isotope measurements of ancient bronze artifacts. The fsLA-MC-ICP-MS technique could be applied to differentiate the high radiogenic lead in bronze artifacts from common lead.