High-precision low-level Cd isotopic analysis using MC-ICP-MS and its application to marine samples from Terra Nova Bay (Antarctica)†

This study presents the development, validation and use of an approach for precise and accurate cadmium (Cd) isotopic analysis at low concentration levels using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The MC-ICP-MS unit used was equipped with a standard sample introduction system, thus using an ICP operated under wet plasma conditions, and Faraday cup amplifiers equipped with a 10¹³ Ω resistor. One-column anion exchange chromatography allowed isolation of Cd with 80–99% recovery and absence of an effect of potential on-column fractionation on the isotope ratio results was demonstrated. Use of both an internal (using Ag) and an external (measured in a sample-standard bracketing sequence) standard was relied on for correction of the bias introduced by instrumental mass discrimination. A long-term precision of 0.09‰ (2SD) for δ^114/110Cd was achieved at a Cd concentration of 10 ng mL⁻¹. The method developed was validated by analysing NIST SRM 2711a (Montana soil) and NRC TORT-3 (Lobster hepatopancreas) reference materials, yielding results consistent with literature values. Subsequently, the method was applied to two Antarctic marine organisms Adamussium colbecki and Trematomus bernacchii, collected during both the 1990s and 2020s, to investigate its potential for identifying changes in the biogeochemical cycle of Cd over time and reveal natural or anthropogenic sources. A preferential uptake of the lighter Cd isotopes in both species was observed, indicated by negative δ^114/110Cd values ranging between −0.24 and −0.09‰. This finding is consistent with previous studies that have reported Cd fractionation during its uptake by marine organisms, with a preference for the lighter isotopes. No significant differences in δ^114/110Cd values were observed between organs of the same species or between the same species collected in the different decades, suggesting minimal Cd isotope fractionation during internal transfer and consistent Cd sources over time. Comparison with literature data suggests that the Cd source in Antarctic biota may be predominantly of natural origin, with δ^114/110Cd values indicating isotopically heavier Cd than that found in Cd-polluted areas. However, further Cd isotope ratio data from various Antarctic sample types are necessary to further evaluate the Cd sources in marine samples.