High performance automated ion chromatography separation for Ca isotope measurements in geological and biological samples

Natural mass-dependent fractionation of calcium isotopes is a promising tool for investigating Ca pathways and cycling in geological and biological materials. But since natural isotope fractionation of Ca appears to be extremely limited (similar to 1.25 parts per thousand/amu), excellent external precision and sensitivity are needed to make full use of its potential. Here, we describe a new Ca purification procedure that consists of a high selectivity automated ionic chromatography separation protocol, which is suitable for Ca isotope measurements by mass spectrometry and applicable to multiple natural matrixes (waters, mineral and organic samples). The analytical progress in this automated technique are multiple: (1) saving time with a minimum of handling, (2) unique operating protocol whatever the nature of the sample, (3) complete separation of Ca from K, Mg and Sr, avoiding isobaric interferences which are critical during TIMS analysis, and (4) Ca separation by peak recognition optimising the full recovery of Ca even if its retention time is shifted from one sample to another. The two latter advantages ensure a Ca recovery yield close to 100%, leading to the absence of any fractionation of Ca isotopes during the chemical clean-up. Thus, this chemical separation will be of special interest for applications not compatible with the use of the double spike technique such as MC-ICP-MS and Ca-40 excesses measurements. Additionally this procedure leads to a twofold improvement of the long-term repeatability of the Ca isotopes determination by TIMS (+/- 0.11 delta Ca-44/40, 2SD) as compared with a classical resin ch emistry protocol and is similar to the best repeatability published so far (+/- 0.10 delta Ca-44/40, 2SD).