Incorporation of U, Pb and rare earth elements in calcite through crystallisation from amorphous calcium carbonate; Simple preparation of reference materials for microanalysis

Miyajima, Yusuke*; Saito, Ayaka*; Kagi, Hiroyuki*; Yokoyama, Tatsunori   ; Takahashi, Yoshio*; Hirata, Takafumi*

Uncertainty for elemental and isotopic analyses of calcite by LA-ICP-MS is largely controlled by the homogeneity of the reference materials (RMs) used for normalization and validation. In order to produce calcite RMs with homogeneous elemental and isotopic compositions, we incorporated elements including U, Pb, and rare earth elements into calcite through heat- and pressure-induced crystallization from amorphous calcium carbonate that was precipitated from element-doped reagent solution. X-ray absorption spectra showed that U was present as U(VI) in the synthesized calcite, probably with a different local structure from that of aqueous uranyl ions. The uptake rate of U by our calcite was higher in comparison to synthetic calcite of previous studies. Variations of element mass fractions in the calcite were better than 12% 2RSD, mostly within 7%. The Pb/Pb ratio in the calcite showed 1% variations, while the U/Pb ratio showed 3-24% variations depending on element mass fractions. Using the synthetic calcite as primary RMs, we could date a natural calcite RM, WC-1, with analytical uncertainty as low as 3%. The method presented can be useful to produce calcite with controlled and homogeneous element mass fractions, and is a promising alternative to natural calcite RMs for U-Pb geochronology.