Matrix-matched quantitative analysis of trace-elements in calcium carbonate shells by laser-ablation ICP-MS: application to the determination of daily scale profiles in scallop shell (Pecten maximus)

Abstract : A micro-scale method has been developed for analysis of trace-element concentration profiles in the calcium carbonate shell of the Great Scallop (Pecten maximus). UV laser ablation at 266-nm coupled with ICP-MS detection was used to analyse daily calcite striae of shell samples to obtain high temporal resolution of trace element incorporation. Analysis of scallop shells was carefully examined to determine the quality of calcium carbonate ablation and calibration. An accurate external calibration method based on matrix matching was developed. Twelve sodium-free enriched calcium carbonate standards containing up to twenty-four elements were prepared, by co-precipitation with aqueous ammonia and NH4HCO3, and subsequently back-calibrated in the laboratory. These CaCO3 standards were found to be homogenous and their use enabled sensitive quantitative analysis (detection limits of a few ng g−1) over a wide range of concentrations (0.1 to 500 μg g−1). Use of these CaCO3 standards was also evaluated by analysis of three calcium-rich certified reference materials. Because calibration was consistent with the certified results, this analytical method is a sensitive tool for analysis of environmental calcium carbonate matrices. Repeated analysis of scallop shell samples collected simultaneously at the same location showed that the trace elements are homogeneously distributed along a stria. The reliability of such in-situ records of biogenic calcium carbonate (scallop shells) is apparent from the inter-individual and inter-annual reproducibility of the trace element profiles.